Compounds of Alkali Metal Anions

By James L. Dye"'

Anions of sodium. potassium, rubidium, and cesium are stable both in suitable solvents and in
crystalline solids. The latter can be prepared either by cooling a saturated solution or by rapid
solvent evaporation. Thermodynamic arguments show that alkali metal anions can probably
exist in saturated solutions of the alkali metals in any compatible solvent. but that below satu-
ration, dissociation into the cation and solvated electrons is favored in highly polar solvents
such as ammonia. The key to solvent-free salts of the alkali metal anions is stabilization of the
cation by incorporation into a suitable crown or cryptand complex. By using such complexes it
also appears possible to produce "electride" salts in which the charge of the complexed cation
is balanced by a trapped electron. The chemical, electrical, and optical properties of salts of the
alkali metal anions and "electrides" could provide useful applications.

1. Introduction present in concentrated metal-ammonia solutions, but there

Alkali metals are exceptionally good electron donors,
tending to form monopositive ions by donation of one elec-
tron to an acceptor atom or molecule. The resultant cation
has a stable inert gas electron configuration with a filled out-
er p-shell. Because of this, the history of compounds of the
alkali metals has been that of the cations and it was long
thought that, except in metals and alloys, only the + 1 oxida-
tion state could exist. Yet the existence of alkali metal anions
in the gas phase has been recognized for 30 years['.21.These
anions were proposed as major species in metal-ammonia so-
lutions in 19651' 41 and in metal-amine solutions in 1969"'.
The isolation and characterization of a crystalline N a -
salt["-'' in 1974 firmly established that the - 1 oxidation state
of alkali metals could exist in condensed phases. This has
opened a new field of research on the properties of these
highly-reducing species both in solutions and in solids. It is
the purpose of this article to describe the current status of re-
search in this field and to speculate on possible future devel-
opments.
2. Properties of Alkali Metals in Solution
The preparation of salts of the alkali metal anions has its
origins in the study o f metal-ammonia solutions and solvated
electrons[x ' I 1 . However, the discovqy of alkali metal anions
may have actually been delayed by the fact that ammonia is
"too good" a solvent so that the dissociation reaction
lies far to the right in dilute solutions and most properties are
only mildly influenced by the cation. This does not mean
that metal-ammonia solutions are simple: quite the contrary;
ion-pair formation, electron spin-pairing and the onset of
metallic behavior occur as the solutions are concentratedlxl.
Because of these complications, alkali metal anions could be
is no specific evidence of such species in this solvent.
2.1. Solutions in Amines and Ethers
When any alkali metal except lithium is dissolved in an al-
iphatic amiae, poly-ether or hexamethyl phosphoric triamide
(HMPA), two prominent optical absorption bands are ob-
served. One, in the infrared region at 1200-2000 nm, is the
relatively metal-independent band of the solvated electron.
The other band, whose position depends upon the metal, sol-
vent and temperature, can be assigned to the alkali metal an-
ion"'. The proof of this assignment has been discussed in de-
tail elsewhere[".7.'2 and will be included here only as
needed for the description of specific systems or properties.
Progress in identifying the species in metal-amine and me-
tal-ether solutions was hampered by low solubility, rapid de-
composition. and the ease of extraction of sodium from boro-
silicate glassl'xl.The problem of low solubility was overcome
by the use of crown ether'"' and cryptand["'' complexing
agents. Extraction of sodium from glass presents a major
problem only at low concentrations and can be completely
eliminated by using a fused silica apparatus. Unfortunately,
problems arising from solution decomposition are still with
us but can be minimized by working with rigorously clean
vessels[*'' and at reduced temperatures.
2.2. Optical Spectra
Each alkali metal anion is characterized by a broad, in-
tense, structureless absorption band which depends upon
metal, solvent and temperature and is strongly asymmetric
on the high-energy side. These features are characteristid5' of
the so-called charge-transfer-to-solvent (ctts) bands[22.231of
other anions such as the halides, hydroxide, amide. etc. The
spectra are also similar in shape and in solvent-'"' and tem-
perature-dependence to those of the solvated electron in var-
ious solvents["] but the absorption maxima occur at higher
energies. Figure 1 shows the spectra of Na ~,K ~,Rb , Cs ~

and e,,, in ethylenediamine'24'. The spectrum of e,;,l> ob-

[*I Prof. Dr. J . L. Dye
Department of Chemistry. Michigan State University tained by pulse-radiolysis"'1 (solid circles) compares well
Eaht Lansing. Michigan 48x24 (USA) with that obtained by dissolving lithium (solid line) in ethy-
 16 14 12 10 09 08
- d [pml
07 06 05
Excited states of the anion might lie above the ionization
limit in the gas phase. yet be observable in solution or in
I I I I I
crystals, either because of a strong perturbation of the con-
tinuum level or because of low probability for direct excita-
tion to the continuum level of the solvent. In fact. auto-ioni-
zation apparently occurs from excited states of the alkali met-
al anions and other anions in solution[2h"I suggesting that
the continuum level lies at lower energies than does the first
excited state. It is probably appropriate to consider the in-
tense absorption band of M in solution and in crystals as
originating from an s to p transition, modified by the pres-
ence of solvent molecules or neighboring ions and including
a contribution from direct bound-continuum transitions["I.
I I I I 1 I
6 8 10
v
12
CcmC 10.~1
14
- 76 18 20
2.3. Conductivity
Fig. 1 . Optical \pectra 01. Li. N d . K. Rh. and C s in cthylrnedianiine 1241 w t h
identification of absorption peaka 0 1 N a . K . R h . Cs and e-<,,,.Solid clr- The conductivities of sodium and cesium solu-
cles are for e ~ , , ,produced
\ by pul\e radiolysir 1251. tions in ethylenediamine""' and methylamine""' have been
measured. The optical spectra show that sodium solutions in
lenediamine. The infrared shoulders obtained for solutions these two solvents consist primarily of Na ' and N a - while
of K, Rb and Cs are attributed to the solvated electron and dilute cesium solutions contain mainly Cs and e,,,,,. The +

the ratio of this absorbance to that of the anions depends differences in conductivity of these solutions are striking-as
strongly on concentration (see Eq. 1 ). The solvent-depend- shown in Figure 3. The rapid drop in conductivity with in-
ence of the peak positions is illustrated by Figure 2, which
compares the peak positions of Na , K - and e,,,,, in var- I
ious solvents. The solvent-dependence of the absorption 3h
maximum of e,,,, correlates in turn with that of I I2'I. ~

154 I , , I I I I I

150 ~ 4kDdA
-6
7,1 111,2-
.0
u

I:"-//
L6-

1 30 - o HMPA o
O,
OEACD ME

DEY'
DIPE
y HMPA
UDME U D E A
THF

Fig. 3. Product of equivalent conductance ( A ) and solvent viscosity (TI) for solu-
tions of Na in methylamine I 3 [30], and ethylenediamine A [29], and of Cs in
methylamine 0 [30]. ethylenediamine x [29]. and ammonia 0 [83].

creasing concentration for solutions containing Cs and +

e,,,,, in the amines resembles the behavior in ammonia and

Maialun, Golden and Ottolenghi[51 showed that the
wavenumber of maximum absorbance of the alkali metal an-
ions varies inversely with the estimated anion radius, in ac-
cord with the predictions of ctts theory. The observed tem-
perature-dependence of the peak position is also predicted
by this We conclude that the absorption spectra
of M in solution are similar to those of other anions.
~
An examination of ctts theory might lead one to conclude
that the excited state bears no relation to excited states of the
isolated anion. This does not necessarily follow. however.
can be readily accounted for in terms of ion-pairing between
Cs+ and e - . The high limiting conductance of e,,,,,, in both
ethylenediamine and methylamine is also similar to the be-
havior in ammonia especially when the appropriate viscosity
corrections are made as in Figure 3. The conductivities and
the similarity in optical spectra thus provide strong evidence
that metal solutions in methylamine and in ethylenediamine
which d o not contain alkali metal anions are similar to met-
al-ammonia solutions. By contrast, the conductivities of so-
dium solutions in methylamine and ethylenediamine show
that the mobility of Na-- is "normal" and that the extent of

588 Anxew. C l e m . In!. Ed. Engl 18. 587-.798 (1979)

ion pairing between Na' and Na is small, as expected for a
large interionic contact distance.
2.4. The Effect of Crown Ethers and Cryptands
One of the major barriers to experimental studies of alkali
metal solutions in amines and ethers is the generally low soi-
ubility. Combined with the ever-present tendency towards
decomposition, this low solubility has made reproducible
measurements difficult. By using crown-ether and cryptand
complexes such as those of [18]crown-6 ( l ) ,and C222, we
[18] crown-6 C r y p t and s
C222, m = n = o = 1
were able to dramatically increase metal solubilities in a
For a cation complexing agent
number of solvents['2.'y~20.3il.
(Cry = cryptand) the equilibrium (2) shifts the equilibrium
(3) to the right, thus increasing the concentration of M - in
M + + Cry 5 M + C r y
2M,,, e M++M ~
the saturated solution. (This also applies for crown ethers as
complexing agent.) When excess metal is present, equilib-
rium (4) determines the relative concentrations of M - and
M * M,,,+e,,, (4)
e,:,,,. In the absence of excess metal, equilibrium (1) governs
the relative concentrations of M - and e,,,. The addition of
a cation-complexing agent shifts reaction (1) to the right by
reducing the concentration of M +. Equilibrium (3) requires
that the product of the activities of M - andfree cation can-
not exceed the limit imposed by the solubility of metal. These
reactions permit a measure of control over the composition
tion of the solutions. The maximum value of the ratio [M -]/
[e,,,,] for a given metal is determined by the solvent and the
temperature according to reaction (4). If this ratio is large,
solutions consisting of primarily complexed M ' and M can - prevent the observation of the N MR signal of M and may
be prepared by maintaining an excess of metal in the prepa-
ration vessel. Alternatively, if K,[*Iis not too small and K2 is
large, the addition of equimolar amounts of complexing
agent and metal can yield solutions whose composition is
mainly complexed M + and e,,,. ,Section 3 considers the
thermodynamics of these reactions In more detail.
2.5. Nuclear Magnetic Resonance
The ability to prepare concentrated metal-amine solutions
(up to 0.2 M and higher) by using crown ethers and cryptands
opened the door to NMR studies of alkali metal a n i ~ n s [ ~ ' . ~ ~ l . r a d i o l y ~ i s ~ ~the
It was k n ~ w n ~ from ~ ~ . NMR
~ " studies with salts that the rel-
ease of Na' from a Na'C222 complex is slow o n the N MR
time scale, so that separate "Na-NMR signals were expected
and found for Na Cry and for Na- . Figure 4 shows the
+ of the absorption maximum leads to the production of sol-
['I KI IS the equilibrium constant for reaction ( I )
Angen G e m . Inl Ed. Engl. I d 587-598 (1979)
spectra obtained in three solvents[331.The calculated diamag-
netic shift of 6 = - 2.6 for Na compared with Na(g)13'.3hlis
-
I
H-
1-1.
I I , I I 1
80 60 LO 20
-s 0 -10 -20
Fig. 4. "Na-NMR spectra of Na ' C222. Na solutions ( ~ I M0) in three m -
vents [33]. All shifts are referred lo Na,,,. Positive shifts are paramagnetic. The
peaks of Na ' C222 at the left are at a = t49.5.T h e peaks of Na at the right dre
at a = -2.
very close to the measured shifts[331 of 6 = - 1.4, - 1.6, and
- 2.3 for Na in methylamine, ethylamine and tetrahydro-
-
furan respectively. This is to be compared with paramagnetic
shifts of 60.5, 72.2 and 50.4 for N a + in water, methylamine
and the cryptate complex respectively. The absence of an ap-
preciable paramagnetic shift for N a - in solution proves that
the solvent is prevented from interacting appreciably with
the 2p electrons by the presence of the outer 2s electrons.
This, in fact, provides the strongest evidence that Na in so- -
lution is truly a n alkali metal anion rather than, say, a sol-
vated cation with two solvated electrons in the vicinity or a
solvated cation attached to a solvated electron pair.
The NMR spectra[331 of Rb in ethylamine and in tetrahy-
-
drofuran (THF) show single lines at 6 = +26.2 and +14.4
ppm respectively relative to Rb(g) while the peak for Cs- in
T H F occurs at 6 = + 52.3 ppm relative to Cs(g). These are to
be compared with values of 6 = +213 and + 348 for aqueous
R b + and Cs' respectively. Exchange effects1"' sometimes
-
be the reason that we have not yet been able to observe K -
by N MR even in solutions whose optical spectra show the
existence of high concentrations of this species.
2.6. Other Solution Properties of Alkali Metal Anions
The rate of reaction of Na with water in ethylenediamine
-
is much slower than that of eSirvand the reaction order in
water is also different(2'.'71. The rate of formation of Na-.
from solvated electrons and Na' has been studied by pulse
~ . 'reaction
~~; is second order w.r.t. el,,,,. The
dependence of the rate on the concentration of Na is com- +
plex and suggests['41that electron-pairing precedes the for-
mation of N a - . Photolysis of M - in the wavelength region
vated electron^'^' 471, sometimes in a spin-polarized
state[40.46.471 (CIDEP). Photoelectron emission has also been
589
 from e,;,,, and from Na in HMPA. These ob-
servations generally support the assumption that alkali metal
anions are new species and not just a combination of the sol-
vated cation and two solvated electrons.
2.7. Ion pairs and "Monomers" in Solution
The electron spin resonance (ESR) spectrum of the sol-
vated electron consists of a single narrow line with a g-value
near that of the free electron. When the electron interacts
strongly with an alkali cation so that appreciable electron
density exists at a metal nucleus with spin I. and when this
electron-cation pair has a long enough lifetime (generally
microseconds or longer) then a hyperfine pattern results with
21+ 1 nearly equally spaced lines[4x"I. Pulse radioly-
sis[iX.52.531 and p h o t o l y ~ i s [ ~studies
'~ in the presence of alkali
cations have shown that the optical spectrum of e,:,,, is
blue-shifted by formation of the ion-pair (also referred to as
an alkali metal "monomer"). The magnitude of this blue-
shift increases as the polarity of the solvent decreases and
correlates well with the electron contact density at the alkali
nucleus as determined by ESR measurements[5". Changes in
the cation-electron contact density and in the spectrum with
solvent and temperature have been attributed to the forma-
tion of solvent-shared and contact ion-pairs"". Although the
sensitivity of the ESR technique permits easy detection of
the monomer species, the equilibrium concentration of mon-
omers, M, in amines and ethers is generally small compared
with M - and e,o,v. Crown ethers or cryptands shift the
equilibrium
M+M+ t e -
for salts of the alkali metal anions (which we refer to as "al-
kalides") was also based on thermodynamic predictions of
their stabilities and we continue to be guided in the search
for appropriate metals, solvents and complexing agents by
approximate calculations of stability constants. Questions
have also arisen about the possible existence of anions of
other metals such as the alkaline earths. I t is a simple matter
to show thermodynamically that the existence of an ion such
as Ca in solution is thermodynamically impossible while
the gold anion, Au -, may well be thermodynamically stable.
In this section some of the pertinent thermodynamic argu-
ments will be given. Some of the predictions can be made
with reasonable accuracy; others are far less certain, either
because key measurements have not yet been made or be-
cause of limitations of the theory of solvation free energies or
lattice energies. In either case, it is often possible to make
reasonably accurate relative calculations which at least per-
mit comparisons among the alkali metals.
3.1. Stability of Metal Anions in Ammonia as Solvent
It is possible to calculate accurate values of AH" and AG"
for the process
from electron a f f i n i t i e ~ [ ~properties
.~~], of the solid and ga-
seous and statistical thermodynamlcs calcula-
tions of entropies['"]. The values of AH',' and AG',' for the al-
kali metals and some other metallic elements at 25 " C are
(5) given in Table lI*].

Table I . Thermodynamic estimates [a] used to Judge the stability of.anions in ammonia to dissociation into metal and solvated electrons

Metal Estimated Electron A ~! A 6:: AH! A G<.,

anion radius Affinity
r (A) 298 K 23X K

Li 2.35 59.8 96.7 67 7 - 65.8 1.x - 1I.X

Na 2.72 52.9 53.4 30 6 - 18 I - 5.6 - 20.2
K 3.27 48.4 39 I 18.2 - 59.3 13.5 - 1.1
Rh 3.39 46.9 36.4 14.4 - 56.3 15.2 0.X
cs 3.55 45.5 30.1 10.9 - 54.9 I x.5 38
Au 2.00 222.7 140.9 109.0 - 61.5 5. I - x3
AL: 2.00 125.7 156.4 125.4 - 46.0 21 4 1.9
cu I .93 118.3 217.5 1x5 7 5.5 72.5 59 0
Ba 3.5 - 52.1 225.4 202 3 137.7 207.9 193 7
PI 3.55 205.3 357.5 320.6 27 I .9 32X 2 3 16.9
Te 2.3 f83.3 I1 0 - 20.x - 156.5 -91.4 - 104.5
Ph 2.2 101.3 91.2 66.0 - X6.X - 14 1 - 29.2
61 2.2 101.3 103.3 12.3 - 14.1 - 8.4 - 21 8
TI 2.1 4X.2 131.5 104.6 - 5x I 12.8 - 14
Sh 2.2 101.3 15X.6 126.3 - 195 45.6 32 5
Sn 2.2 120.6 179.0 152.2 I.o 7I .4 51.3

[a] All values given in kJ mol I: AH:= 247-535(1/r); Ad:= 334- 51 I ( I / r )evaluated by fitting data for the halide ions (see text).

to the right in the absence of excess metal. Although the con- If the solvation free energy of M,, is more negative than
centration of monomers is low, they may play important that of e;, by an amount equal to or greater than that given
roles in the exchange kinetics of complexed M i and M and in Table 1 then the reaction
in the rate of decomposition of metal solutions.
e , , , + M,., - M,,, (7)
3. Thermodynamic Considerations
metal anions in ammon- ['I Many o l t h e thermodynaniic ealimates described in this article have not been
The proposed existence Of previously puhliahed. Details of the calculations arc dvallahle f'rom the author on
ia[3.41was based on thermodynamic arguments. Our search requebl

590 Angew. Chem. Inr. Ed. Engl. I H . SH7-398 (1979)

is feasible and we can expect M - to be stable to dissociation
into the (solid) metal and solvated electrons. According to
the Born e q ~ a t i o n l " both
~ the Gibbs free energy of solvation
and the enthalpy of solvation of an ion are inversely propor-
tional to the ionic radius. Since the Born equation is based
on a continuum model and fails to account for specific solva-
tion of the ions, it is not appropriate to use it directly. A bet-
ter procedure is to use the known free energies and enthal-
pies of formation of CI-, Br- and 1- in ammonia[5x1togeth-
er with the thermodynamics of formation of the correspond-
ing gaseous anions to calibrate the dependence of the solva-
tion enthalpy and Gibbs free energy upon radius. Specifical-
ly, AC$ and AH'; for
are linear functions of the reciprocal of the anion radii of
CI-, Br . and I -. These thermodynamic functions were ob-
tained by combining the reactions
XI,] +el,, + XI,,
The values of AG?; and AH': were obtained from the
tabulation of Latimer and Jolly[5x1and are based upon
AG: = 0 and AH'; = 0 for H in ammonia. The values of AGO
+
for reactions (10) and (1 1) were obtained from known atomi-
zation free energies and enthalpies["I of the halogens and
their electron affinities[s41.By assuming that the solvation
free energy and enthalpy of other anions depend upon radius
in the same way as those of C1-, Br- and I - , we can calcu-
late AGA and AH': for any anion if we know its radius. Fol-
lowing the suggestion of Malalon, Golden and Ottolenghi'51
we can estimate the radius of an alkali metal anion by sub-
tracting its ionic radius from the interatomic distance in the
metal. The radius of Au- (2.0 A) was obtained by subtract-
ing the radius of Cs' from the cesium-gold distance in the
ionic compound CsAulSY1.The values'sxl AG= - 182 kJ
mol ' . A M , l = - l 5 9 k J m o l - I f o r N a ' i n N H 3 a t 2 5 " C a n d
AH','= - 182 kJ mol-' for eYNH,,combined with A G : 2 ~ 0 . 0
at 25 oC16cr1for the process
gives AH':3= AGy3 = - 182 kJ mol- I for
at 25 "C based upon the convention that the enthalpy and
free energy of formation of HG,,, are zero. Addition of
reactions ( 6 ) , (8) and (13) gives reaction (7). The values of
AH'; and Ad: at 25 " C and Ad: at -35 "C for a number of
metallic elements are given in Table I. The results show that
the reaction of solvated electrons with metal to produce am-
moniated metal anions with filled outer s-orbitals may be
thermodynamically permitted for all of the alkali metals and
for gold1*Iand silver. It appears that Cu would not be stable
to dissociation into Cu,,, and e,;,,.
Angen: ('hpiit Int. Ed. Engl I X . 5x7-598 llY7Y)
For ions which do not have the added electron in an s-or-
bital, the calculations predict stability for T e - , Pb , Bi .
and TI- . The first three of these elements do form anions in
ammonia'h'.h21which have also recently been isolated in crys-
talline salts[" "I, but in these cases the anions are polymeric
rather than monomeric. Salts which contain polymeric an-
ions of antimony and tin have also been i ~ o l a t e d ~. ~0ur'~~'~~~~
calculations indicate instability of monomeric Sb and Sn - -
in ammonia but the addition of metal-metal bonding would
stabilize polymeric anions.
The existence of detectable concentrations of such ions as
Ba- and Pt- in ammonia is clearly impossible from a ther-
modynamic viewpoint. In the former case, the negative elec-
tron affinity of barium shows that Ba- is not even stable in
the gas phase. On the other hand, while platinum has a large
electron affinity the lattice energy is so great that conversion
of Pt,,, to Pt- by the action of solvated electrons is not ther-
modynamically permitted.
3.2. Dissociation of M - to M + and Solvated Electrons in
Solution
The calculations described above were made for ammonia
solutions because we have sufficient data to calculate Gibbs
(11)
free energies and enthalpies of formation of ions in ammon-
ia, but not in amines and ethers. Similar calculations could
be made for amine and ether solvents if sufficient solubility
and/or e.m.f. data were available. Yet ironically, we have no
XpecQ'ic evidence for the existence of alkali metal anions in
ammonia. Let us examine the predicted concentrations for
the most favorable case, that of Na -. From the data in Table
1 we can calculate that for the reaction
at - 35 "C, K I 4= 3 x lo4. However, in a dilute solution away
from metal we must also consider the equilibrium
for which K I 5 = 4x lo-' M *. This predicts that at a sodium
concentration of M (neglecting the effect of activity
coefficients) the ratio [Na-]/[e-] should be about 0.15. If the
optical spectrum of N a - were appreciably different from
that of e in ammonia as it is in amine and ether solvents,
~
then the presence of this concentration of Na would be eas-
-
ily detectable. Certainly, upon addition of a sodium salt the
presence of N a - should be observable. However. no promi-
nent optical band of N a - has been observed either in the
presence or absence of sodium salts. We must conclude that
either the calculation given for N a - in Table 1 is in error by
15 kJ mol-' or more, or the optical band of Na is shifted
into the infrared in ammonia as originally suggested by
Golden et al.[31.We conclude that, while such calculations as
these cannot be used to determine concentrations, they do
demonstrate that the existence of alkali metal anions in am-
monia, amines, and ethers is not prohibited on thermody-
namic grounds.
['I W. J. Peer and J. J. Lagowki [J. Am. Chem. Soc. 100. 6260 (1978)) have re-
cently shown that Au can be formed in liquid ammonia.
591
3.3. Stability of Metal Anions in Amine and Ether Solvents as good a solvent as water, means that the gas phase com-
plexation reaction
Alkali metal solubilitiesl2'I and s p e ~ t r a l * ~ . have
~ ' ] been
MfLi+ Cry,,, M + Cry,,, (16)
measured for ethylenediamine solutions at 25 "C. The extinc-
+

tion coefficients of N a - and e5& in ethylenediamine are is strongly exothermic and highly favored. There are no di-
8.2 x lo4 and 2.0 x lo4 M ' c m - r e s p e ~ t i v e l y " ~ -These
'~~. rect data for this reaction, but indirect methods can be used
measurements permit estimation of the equilibrium con- to evaluate AH:, and AG:, for the reaction
stants K , , K 3 , and K, for ethylenediamine as solvent (see Ta-
ble 2).
Cry,,, + M,,,, + M,,,, + M :Cry Mi,,, (17)

Although (excluding Li-) N a - is most stable and K - is in which M, and M, may be the same or different. If
least stable relative to e,;,, in the presence of excess metal, AG';, is negative then the salt M: Cry M; is stable to decom-

Table 2. Estimation of equilibrium constants K , , K , and K7 for reactions of alkali metal anions in ethylenediamine at 25 "C from optical spectra and solubiltties.

Metal Solubility Path lenght Absorbance Data Used Ref. K, K ; [aj K7

(M) icm) A, A hl (M '1 (hl I)

Li 0.29 01 2 <0.05 [bj (241 > 4 x 10 t2x10 ' c7

Na 2 . 3 9 ~in ' 10 0.09 0.Y I 1691 3x10 1 . 4 ~ 1 0" 220
K 1.04~10 I .0 2.0 0.46 [c] (691 I.hX10 6 2.7 x 10 ' 41
0.01 0.2 0.6s (241 2.3 x 10 '' 2.7x 10 ' 3.4
'
Rb

cs
1.31~10

5.4x 10
1 .0
01
0.01
0.84
0.36
0.6
0.40
0.6K
0.9
1691
1241
1241
1 . 7 ~ 1 0"
1 O X 10 '
4x10
43x10 '
4.3 x i n
7x10
- 50
20
5

[a] K,= K , KS. [bj Estimated conc. of L1=3 x 10 'M. [c] In the presence of' I x 10 ' M added K ' .

the concentration of M in the saturated solution increases
regularly from N a - to C S C . The dissociation of M to
M' + 2es;,, is least likely for N a - and most likely for K - .
This apparently anomalous position of potassium solutions
seems to reflect extra stabilization of the solvated electrons in
the presence of K +,perhaps oia ion pairing. Such an effect
has actually been observed both by the addition of a potas-
sium salt to a solution of sodium in ethylenediaminel"] and
by pulse radiolysis The appearance of the spectral
peak of the solvated electrons occurs in this case but not
when Rb or Cs are added.
+ +
Solubility and spectral data in other solvents are too sparse
to permit evaluation of equilibrium constants. However, it is
clear that the values of K 2 increase while K , and K 3 both de-
crease as the solvent polarity decreases. Thus, all metals ex-
position into its components Cry, M, and M,. By adding all
of the AH" and AG" values for the reactions listed in Table 3
one obtains AHY7 and AG?,. While the absolute values
of AH:', and AG:7 given in Table 4 may be in error by as
much as t 5 0 kJ because of errors of measurement and the
various approximations made, their relative values should be
much more reliable. Since we can prepare the crystalline salt
N a + C 2 2 2 N a - , even in the presence of an excess of sodium
and cryptand, it appears to be thermodynamically stable.
The calculated value of AG?, for this salt is +32 kJ mol I
which is within the estimated absolute error of the
value A G ~ , s O required for thermodynamic stability. It ap-
pears safe to assume that any proposed salt with a value
of AGO, equal to or more negative than that of the reference
salt Na C222 Na is likely to be thermodynamically stable.
+

cept lithium when dissolved in ethylamine show primarily
the optical band of M - with little contribution from e , , , .
Based upon the effect of C222 on the optical spectrumi701we
estimate that K , < iO-*O for sodium in tetrahydrofuran.
Therefore, solutions of sodium in this solvent, even in the
presence of excess cryptand consist essentially of
Of course, these calculations do not preclude decomposition
via destruction of the cryptand moiety, a process which we
have found to be very common.
A critical quantity in these calculations is the interionic
distance in the crystalline salt. The sum of the calculated ra-
dii rN1 iCr,and rNa is larger than the measured distance in
~

Na'C222Na- with no detectable solvated electron concen- the salt Na C222 Na by 14%.This could be caused by lack
+

tration. By contrast, solutions of potassium in tetrahydrofu-
ran with cryptand contain largely K'C222K- when excess
potassium is present, but mainly K' C222e,;,, when an
equivalent of cryptand is present[701.
of sphericity of the cryptated cation, an error in the estimate
of its size or that of N a - , and/or compression of these rela-
tively "soft" ions in the crystal. The cation-anion distances in
Na+C2221-[761and K'C222I- are within a few percent
of those calculated on the basis of the ionic radius of I - and
the radii of Na C222 and K C222 calculated from the li-
+ +

3.4. Stability of Metal Anions in Crystals
Attempts to grow crystals containing alkali metal anions
were based upon their stability in solution, and the realiza-
tion that stabilization of the cation by its inclusion in a cryp-
tand cavity might prevent the spontaneous recombination of
M' and M - to form the metal. The fact that alkali cations
are strongly complexed by the appropriate cryptand, even in
gand thi~knessl'~'.Therefore, the most likely source of error
in the estimate of the interionic distance in NaiC222Na- is
an error in the estimated radius of N a - or neglect of the
compression of this ion and of the cryptated cation in the
crystal. In order to compensate for this reduction in inter-
ionic distance, all of the calculated anion radii were reduced
by 14% in computing the lattice energy and entropy in step
(h) of Table 3.

592 Angew. Chem. In(. Ed. Engl. I X . 587-598 (1979)

Table 3. Steps in thermodynamic cycle used to evaluate AH';, and AS:',.
-
Redction Ytep Origin of ddta or estimate Typical
data
source

Enthalpies of complexation and equilibrium constants 1711

Solubility of cryptand a s a function of temperature. enthalpies of solution of pure cryptand in water Ibl
At' and AG" of atomization plus ionization potentials of M,,,. Use Sackur-Tetrode equation for entropies [55. 561
of gaseous speciea.
Tabulated hydration enthalpies and free energies [721
Born equation plus estimate of size of M ' Cry from ligdnd thickness [57. 73. 741
Sum of a-e
AH" and AG" of atomization plus electron affinity of M,,,, and calculation of entropy as in (c) above 154. 551
Kapustinskii equation far lattice energy; AS" from si7e and comparison with alkali m e t d halides [a] (74. 751
Sum off. g, and h

[a] A plot ol.AS(:for formation of alkali halide lattices from the ga7eoua ions L'S ( r M t + r x - j ' is linear, following the equation A$:= - 47.8 - 29.2 ( r M b + r x ) I . while for
tlie alkaline earth5 tlie equation is AS:= -72.2-53.6 ( r M ?I + r x ) ' ( S i n J K ' mol '.r in A).
[b] Data not available so AHA=AC,'=O.O was used in preparing Tables 4 and 5 . Recent calorimetric measurements give AH;= - 24.5 kJ mol ' 1 M. H . Ahrohum. Univer-
sity 01. Surrey (England). private communication. (1979).

Calculated values of A H o and AG" for steps (0,(h) and (i)
of Table 3 are given in Table 4 for a few selected salts. Calcu-
lations involving the cryptated alkaline earth cations in-
cluded the necessary valence corrections but are probably
less certain than those for the alkali metals. Nevertheless,
modynamic stabilities of salts of the alkaline earth cryptates
are particularly striking. In the following sections we will de-
scribe our progress in the preparation of "alkalide" and
"electride" salts and speculate about possible future develop-
ments.

Table 4 I:stimated thermodynamic data [a] for assessment of the stability of some crystalline salts of the type M: Cry M ,
( M y =M,. M,#M,) and M + C r y e - at 25 "C. The subscripts f, h. and i refer to the corresponding reactions in Table 3.

M:CryM. AG,' A q:
M'Crpe

Na ' C222 N a 259 255 - 323 - 258 - 10 28

LI ' C21 I LI 245 226 - 356 -291 - 14 2
K ' C222 K 23 1 227 - 303 - 238 - 33 6
K C222 Na 23 1 227 - 322 - 257 - 38 0
Ba' C222(Na )? 715 72 I - 966 - 866 - 197 -114
K ' C222e 23 I 227 - 294 - 229 - 63 - 3
Li ' C21 I Au 245 226 - 373 - 307 13 27
Ba' C?22(e 715 72 I - 880 - 782 - 165 - 61

[a] All values in kJ mol I. AM,' and AQl not included (see however footnote [b] of Table 3 )

they indicate that salts such as Ba2+C222(Na-)* should be Table 5. Selected estimated values of the enthalpy and Gibbs function (in kJ
thermodynamically stable. mol ' j at 25 'C for the formation of crystalline salts of type M : C r y M , or
MCrye from the metal and the cryptand [a].
These calculations also provide estimates of the thermody-
namic stability of " e l e ~ t r i d e s " ~ ~T~ol . calculate and :
M Cry M; A B ' [b] AG" [b]
M'Crye
AGVx for the process
Li C211 Na - 41 - 19
Cry,,, + M,., + M Crye,,
+ (1 8) Li ' CZI 1 K - 35 - to
Li ' C211 Cs - 33 - x
we assume that the electron occupies the octahedral holes in Li ' C211 e - 74 - 29
a closest-packed lattice of cryptated cations. Therefore the Li ' C211 H 19 58
Li C211 Ag 26 41
effective "radius" of the trapped electron is 0.414rM+Cry and
Li C211 Cu 85 99
the lattice energy is assumed to be the same as that of a salt N a C222 Li
+
19 51
in which a hard monovalent anion just fits into the octahe- N a ' C222e - 35 26
Na C221 Na - 5 17
dral hole. Compression of the packed cations or delocaliza-
+

Na C221 e
+ - 33 II
tion of the electrons would be expected to predict even Ba2+C222(Li.j 2 - 197 - 120
greater stabilities. The conservative estimates given in Table Ba' ' C222(Cs j? - 136 - 51
Ba' ' C222(Au )? - 197 - 123
4 suggest that "electrides" should be stable. The values Ba' ' C222(Ag )2 - 188 - I I3
of AH:',, AG:)6, AH?8, and AG:, for a number of other possi- Ba' ' C222(Cu )> - 134 - 59
C a l i C221 (Na j z - 177 I15
ble compounds are given in Table 5 . Ca' C221 (e j.
-

+ - 154 - 70
At the very least, the results given in Tables 4 and 5 for a Cs'C322Cs - 2 30
variety of crystalline salts of "alkalides" and "electrides" Rb ' C222 R b - 28 I2
suggest that this field is potentially a very rich one for the [a] Values of AM2 and Ad: not included (however. see footnote [b] i n Table 3).
synthesis of a variety of new compounds. The predicted ther- [bl Reaction: Cry,,,+M,,,,+M,,,,-M:CryM, orCry,,,+M,,,-M ' C r y e , ~ , .

Angeu. Chem. Inr. Ed. Engl. 18. 5N7-5YH (1979) 593

 4. Solid Compounds Containing Alkali Metal Anions
By late 1973 the evidence for alkali metal anions in solu-
tion was very strong, and thermodynamic estimates indicated
potential stability of crystalline ionic salts of the type
M 'CryM -. Rapid evaporation of methylamine or ethylam-
ine from concentrated solutions of sodium or potassium in
these solvents in the presence of cryptand C222 left deposits
of metallic-looking gold-colored films on the glass walls.
Upon cooling a solution of Na+C222, N a - in ethylamine
( = 0.1 M) from + 5 " C to dry-ice temperatures, a gold-colored
powder precipitated from solution. Slow cooling resulted in
the growth of hexagonal crystals of the salt Nat C 2 2 2N a -.
Analysis[61and a crystal structure determinationl7]confirmed
the existence of this first solid compound containing a n al-
kali metal anion. The isolation and characterization of other
members of this class of compounds has been hampered by
difficulties with stabilities and with finding the proper sol-
vents for crystallization, but recently we have made consider-
able progress in this area.
4.1. Preparation and Characterization of Na +C222Na
4.1.1. Preparation of Powdered and Crystalline Forms
The preparation of this salt is relatively simple provided
one pays close attention to solvent purity and cleanliness of
the glassware. The type of vessel used is shown in Figure 5.
Na
A / C I
O D D fold axis; filled-in circles represent the "top" Na ions: open circles the bottom
W ones. Triangles represent 0 atoms, squares represent CH-. groups The two N
Fig. 5. Apparatus for the preparation of the crystalline salt Na ' C222Na
A lo G see text.
The sodium, previously transferred under vacuum into small
diameter glass tubing is inserted into glass tube A after scor-
ing the metal-containing tube with a glass knife. Heat-
shrinkable Teflon tubing B is used to connect tube A to side-
arm C. Cryptand is then introduced into vessel G and the
entire apparatus is evacuated. Then the tube containing sodi-
um is shaken into the flexible connection B between A and
C, broken under vacuum and moved to the constriction. A
vacuum seal-off is made behind the metal sample and with
the vessel re-attached to the vacuum manifold, metal is suc-
cessively distilled into vessel E through two or three constric-
tions while pumping (=. torr). (With volatile cryptands
vessel G must be cooled during this operation.) Solvent suffi-
cient to produce about 0 . 0 5 ~cryptand is condensed in G,
the cryptand is dissolved and the solution is transferred into
E and allowed to contact the metal mirror at 0 C for a few
hours. The solution is then poured through the frit F into G
and cooled to - 78 "C, resulting in the precipitation of fine-
ly-divided crystals of Na C222 Na To improve the yield,
+
the supernatant blue solution is poured from the crystals at
- 78 " C back through the frit F into E for further agitation
594
on the metal at 0C. After pouring the supernatant liquid
into E for the last time it is distilled into a waste flask and
either diethyl ether or n-pentane is condensed on the salt in
order to remove any unreacted cryptand or other organic-
soluble impurities. Provision is usually made on vessel G for
transfer of the washed salt into a number of tubes which can
be individually sealed-off under vacuum. Crystals of
Na+C222Na- up to zz 1 mm in diameter can be grown by
slowly cooling a solution which is formed by redissolving the
salt in ethylamine.
4.1.2. Crystal Structure of N a C222 Na +
In its gross features, the crystal str~cturel'~
of this salt may
be viewed as hexagonal closest-packing of the large crypt-
ated cations with the smaller N a - ions occupying the octa-
hedral holes. The cryptand forms a cage for Na with three- +
fold symmetry and a n anti-prismatic arrangement of the
ether oxygens. Views down the three-fold axis and side-on
are shown in Figure 6. The shape of the cryptate moiety and
relative positions of N a ' and N a - are similar to those in
0 0 0
0 0
0
0 0 0 0
a1 bl
Fig. 6. Views of the structure of Na 'C222Na j?]. (a) Looking down the three-
~
atoms and Na' are co-linear at the center. Solid lines connect atoms above the
center; dotted lines below the center. (b) Perspective side-view of the structure.
[74]
N a C222 I [761. The closest Na to Na distances are 8.83
+ -
A in the packing planes perpendicular to the three-fold axis
while the closest distance between N a - ions in different
planes is 11.O A.
This could result in considerable anisotropy
of those properties which depend upon the distance between
anions such as the electrical conductivity.
4.1.3. Properties of N a C222 Na
+
Crystals of this salt frequently grow as thin hexagonal
plates with shiny metallic-looking faces. Their color at liquid
nitrogen temperature is bright yellow-gold, which darkens
reversibly to a yellow-bronze appearance at room tempera-
tures. The crystals melt with decomposition at 83 " C to yield
gray particles suspended in a clear fluid. Analysis after cool-
ing shows that most of the cryptand remains intact and ap-
parently sodium metal is released upon melting. By contrast,
crystals left in evacuated tubes for several days at room tem-
perature and under ambient light conditions darken irrevers-
ibly, apparently with decomposition of the cryptand. When a
sample was kept in the dark at room temperature for three
weeks, no apparent decomposition occurred, but the appar-
ent photosensitivity has not yet been investigated further.
AnKen.. Chrm Int. Ed. EnRl I K . 5X7-598 lIY701
 Packed powders of Na C222 Na have the temperature-
+ -
dependent electrical conductivity expected for a semiconduc-
tor. As shown in Figure 7, logp u s l / T gives a straight line
over six decades of resistance where p is the specific resist-
ance. The magnitude of the resistance depends upon the
packing pressure and decreases with time as the sample an-
neals. Considering this salt as a semiconductor gives a band
1L c t
t 1
Fig. 7 Semi-log plot of specific resistance of powdered samples of
Na C222 Na wrsu.7 the reciprocal of the temperature. Sample A was relatively
loosely-p;icked. The data shown for the tightly-packed sample B were measured
at both increasing and decreasing temperatures [SZ].
gap of 2.4 eV. This salt is diamagnetic, as indicated both by
ESR studies and by static susceptibility measurements. No
magnetic anomalies have been found between 300 and 4.2 K.
The ESR spectrum shows only an extremely weak signal
probably caused by trapped electrons.
4.1.4. The Optical Spectrum of Thin Films of
Na C222 Na
+ -
Powdered or crystalline samples of this compound can be
dissolved in a number of amines and ethers to give deep blue
solutions. Upon cooling such solutions (except in methyl-
amine and ammonia) the salt precipitates. When solutions in
methylamine, ethylamine or T H F are rapidly evaporated,
the walls are covered with a thin film which appears gold by
reflected light and blue by transmitted light. The absorption
spectrum of such a film is shown in Figure 8. In all cases with
this compound the three distinctive features shown in Figure
8 were observed[7x1. The major peak at 15400 cm- (650 nm)
is characteristic of N a - in solution[] and probably arises
from a 3 s to 3 p transition, modified by crystal-field effects.
The origins of the pronounced shoulder at 18 900 cm - - I and
the small but distinct peak at 24500 cm- are unknown al-
though the latter could arise from a bound-free transition
corresponding to the band-gap of 2.4 eV shown by conduc-
tivity. Figure 8 also shows that the gold-colored film formed
by using [ 1 81crown-6 in the presence of solvent vapor has the
major absorption band at 15400 cm-I but shows neither the
extra peak at 24500 c m - nor the shoulder at 18900 cm-I.
The spectrum shows clearly why crystals of NaC222Na-
appear metallic by reflected light. The high absorption in the
near-infrared and sharp cutoff in the visible mimic the plas-
ma absorption of metals. This can lead to a striking metallic
appearance even for nonconducting ~ r y s t a l s [ ~ ~ l .
lot n
?
1_ I0 5 I
L
.
.
..
.
..
.
P
,... .__..
...
.......
./
I I /
5 10 15 20
5 [crn- 10P I - 25 30
Fig. 8. Absorption spectra of a thin, solid solvent-free film of Na C222Na
(solid line) 1781 and of a film of Na 18C-6 Na containing some methylamine
(dotted line) [Sl].
4.1.5. Summary of the Properties of Na C222 Na - +
The structure and properties of the salt NatC222Na- in
the crystalline state and in solution, confirm that N a- is a
genuine spherical anion with two electrons in the 3 s orbi-
tal. Were it not for the tendency of N a - to donate electrons
to any available acceptor, a variety of salts could probably be
prepared. However, stability requires that the counterion be
extremely reluctant to pick up an electron. Any bare metal
cation would probably be reduced by Na- and we will prob-
ably be forced to continue to use complexed metal cations or
perhaps such species as tetraalkylammonium cations. While
the latter will probably not pick up the electron by simple at-
tachment, it is known that solvated electrons can react with
small tetraalkylammonium ions, breaking the C N bond.
Therefore, salts such as R4N Na may not be stable.
+
4.2. Other Salts of Alkali Metal Anions
The crystalline compound described in the previous sec-
tion can be prepared either by crystallization from a solution
containing largely Na C222 and Na - or by rapid evapora-
+
tion of solvent from such a solution. By controlling the com-
plexing agent, metal, and solvent, one can prepare a wide va-
riety of concentrated solutions containing M Cry (or M + +
crown ether), MY and/or e,,,. The metals M, and M ymay
be the same or different. In this section we describe some (as
yet incompletely characterized) solids prepared either by
crystallization from such solutions or by rapid solvent evapo-
ration.
4.2.1. Solids Prepared by Crystallization
The only crystalline solids which we have prepared to date
contain the cryptand C222 with various alkali metals-no
crystals have been made with other cryptands or with crown
ethers, nor have any electrides been crystallized. However,
there seems to be no fundamental restriction on the prepara-
tion of such compounds if one can find the appropriate sol-
vent and conditions for crystallization.
In addition to the salt of Na-, we have prepared other
crystalline solids which appear to be K C222 K -, +
KtC222Na-, RbC222Rb- and C s + C 2 2 2 C s - . The
methods of preparation are similar to those used for
Na C222 N a - (s) except that isopropylamine was used rath-
+
er than ethylamine for salts of K -, R b and Cs . All of the
- ~
595
crystals have a metallic appearance which ranges in color
from light gold for Na C222 Na - to greenish-gold for
+ tained largely M + cryptand (or M + crown ether) and sol-
K C222 Na - to dark copper-bronze for Cs C222 Cs -. So-
+ +
lutions containing K - , Rb-, Cs- and e,;,, are much more
subject to irreversible decomposition than are those contain-
ing Na -. This makes it difficult to prepare crystalline salts of
these anions since all solution manipulations must be done at
low temperatures. Once the solvent has been removed, how-
ever, all of the crystalline solids prepared so far seem to be
reasonably stable and it is likely that we will be able to han-
dle them and characterize them in much the same way as for
Na+C222Na-.
4.2.2. Preparation of Thin Films by Solvent Evaporation
By adjusting the solution stoichiometry and flash-evapo-
rating the solvent (practical only with highly volatile sol-
vents) it is relatively easy to prepare solvent-free transparent
films or powders whose spectral indicate the
presence of M and/or e -. Such films have been prepared
-
and films by solvent evaporation from solutions which con-
vated electrons[]. The ESR spectra of such powders consists
of a very intense narrow line at the free-electron g-value,
suggesting the presence of trapped electrons and extensive
motional narrowing of the ESR signal. Recently Harris and
LugowskiIXol observed narrow ESR lines from solids pro-
duced by freezing metal-ammonia solutions which contained
[18]crown-6. They attribute the signal to an ammoniated
electron in the vicinity of a complexed cation. In our case,
solvent-free blue solids are obtained so that the electrons can
no longer be solvated but may simply occupy the anion sites
in the crystal lattice. We refer to these solids as electrides
although the disposition of the electrons with respect to the
complexed cations is unknown.
We have measured the absorption spectra of electride
films with both cryptand C222 and [18]crown-6 as complex-
ing agents (cf. Fig. 9)[R1.Often the infrared band which we

from solutions of all of the alkali metals in methylamine in

the presence of both crown ethers and cryptands. Films
which show optical bands of M - appear blue by transmitted
light and vary in color from gold to dark-bronze by reflected
light, depending on the metal, while films which have only
an infrared band (presumably the absorption band of trap-
ped electrons) appear blue by transmitted light and very
dark blue-black by reflected light.
Attempts to prepare crystals or powders by slow solvent
evaporation have been generally unsuccessful, with irreversi-
ble decomposition usually occurring instead of precipitation
of the desired compound. Solutions and solids that contain
[18]crown-6 tend to be more stable to irreversible decomposi-
5 10 15
3 [cm
20
- 25 30

tion than those that contain C222. However, in the former Fig. 9. Spectra of solvent-free thin electride films produced by rapid evapora-
solid films of N a + 18C-6Na- also require the pres- tion of methylamine from solutions of K C222e,,, (solid line),
Cs 18C-6e,,, (dotted line) and K tXC-6K (with e,,>,?)(dashed line) [Xl].
~

ence of some solvent. Removal of solvent leads to the forma-

tion of solid sodium and [18]crown-6, without apparent de-
composition of the crown ether. Evidently the axial posi-
attribute to trapped electrons is accompanied by an M - ab-
tion(s) in the N a + 18C-6Na- salt must be occupied by sol-
sorption. In some cases the relative intensities of the two
vent in order for the salt to be stable. It is interesting that
bands shifts in favor of M - as the solution is allowed to con-
films prepared by evaporating solutions containing
tact excess metal[7x1(cf. Fig. 10). In addition to the elec-
[18]crown-6 and either K, R b or Cs give spectra which do not
tride band at 7400 cm- and the band of M - , intermediate
change when all of the solvent is removed.
absorption peaks of unknown origin are often observed (cf.
Fig. 9).
4.2.3. Absorption Spectra of Films
Films prepared by evaporation of methylamine from solu-
tions with stoichiometric amounts of M + , C222 and M - 5. Speculation about Properties and Future
(M C222 M --) show strong absorption bands which are
+
Potential
characteristic of the anion. The shoulder and extra peak seen
with films of Na C222 Na are not observed for any of the
+ - Since we have only limited information about the struc-
other metals. Indeed, when films are prepared from solutions ture and properties of alkalide salts, and even less informa-
of K C222 Na the peak of Na is a single narrow band.
+ - - tion about electrides, it is difficult to predict in what ways
The origin of this change in spectrum and that obtained with these substances might be useful. Certainly, as examples of a
[18]crown-6 (see Fig. 8) remains a mystery although we ex- new oxidation state of a whole family of elements, alkali me-
pect a change in crystal structure from NaC222Na- to tal anions are fundamentally interesting. The strongly reduc-
K C222 N a - or to Na 18C-6 Na -. Since we are now able
+ +
ing nature of these compounds may prove useful in syn-
to prepare crystalline samples of K+C222Na-, it may be theses, and the solid-state properties may provide useful ma-
possible to determine the origin of these spectral differ- terials in such areas as semiconductor behavior, photoelec-
ences. tron emission, photoconductivity, etc. In this section we will
Even before the isolation and characterization of speculate about the nature of these compounds and indicate
Na C222 Na -, we had prepared dark blue solid powders
+
some areas of potential usefulness.

596 Angew Chem. Inr. Ed Engl. I X . 5117-59H (1979)


5 10
i;
15
Ccm- 10.~1 -
20 25
Fig. 10. Spectra of solvent-free thin films produced by evaporation of methyl-
amine from solutions containing cryptand C222 and various relative concentra-
tions of potassium [78]. Spectra for progressively higher concentrations of potas-
sium are in the order, dashed line (electride), solid line (mixture), and dotted
line K (potasside).
5.1. Solution Properties
The use of crown-ether and cryptand complexing agents
makes it possible to prepare concentrated solutions contain-
ing either M or e,;,, in a variety of amine and ether sol-
~ in the dark. Even its reactivity with air is not as great as we
vents. For example, a solution of 0.1 M sodium in T H F can
be prepared by using the cryptand C222. Since this solution
contains mostly Na+C222 and N a - and very little e,,, it
might be useful for two-electron reductions. If a one-electron
reductant in this aprotic solvent were desired, a solution of
potassium with an equivalent quantity of the cryptand C222
would produce K+C222 and e,iiV with little interference
from K .
5.2. Possible New Compounds of Alkalides and
Elec trides
The thermodynamic estimates described in Section 3 sug-
gest that compounds such as Ba+ +C222(Na-)2 should be
thermodynamically stable. Similarly, we predict that solid
compounds containing Li- should be stable. The present
challenge is to find appropriate synthetic routes to such sub-
stances. In solution, Li- tends to dissociate into Li and
e,,,. Perhaps a direct vapor-phase reaction or reaction in an
inert matrix would avoid some of the problems associated
with the use of a polar solvent to dissolve the reacting spe-
cies. One of the problems which we have encountered in
working with lithium and the alkaline earths is the inability
to purify these metals by distillation in glass or quartz. As a
result, solutions tend to be unstable. Distillation of these
metals directly into the apparatus from a metal container
might eliminate some of these difficulties.
It should be possible to substitute other cations for crypt-
ated cations provided they are non-reducible. Long chain
tetraalkylammonium ions seem attractive at present since
they are stable in solution in the presence of Na-. We are at-
tempting to find suitable conditions for metathesis reactions
in solution such as
MCryM-+R,N+X- + M+CryX,J+R,N+M- (19)
If tetraalkylammonium alkalides could be prepared, they
might eliminate one of the major barriers to practical utiliza-
Angew Chem In1 Ed Engl I8 587-598 ( I g 7 9 )
tion of alkali metal anions-the complexity and cost of cryp-
tands.
If the solids which we call electrides prove to be stoi-
chiometric compounds with one trapped electron for each
cation, then it might be possible to prepare a variety of elec-
tride salts such as Bat +C222(e-)2. The increase in electron
density in such compounds compared with M C222 e + ~~
might be enough to give them the properties of expanded
metals, similar to the metallic compound Ba(NH,),[. The
optical and ESR properties of uni-univalent electrides
such as K C222 e suggest that the electrons are largely lo-
+ -
calized, perhaps in the traps formed by the octahedral holes
between closest-packed cations. As the electron density in-
creases, enough electron-electron overlap may occur to give
metallic behavior.
5.3. Possible Uses for the Solid Compounds
Whether the semiconducting properties of Na C222 Na
and similar salts of the other alkali metal anions will be use-
ful depends primarily on their stability. It now appears that
the parent compound is stable at room temperature in uacuo
first thought. For example, a compressed pellet of powdered
NaC222 N a - remained gold-colored and shiny in air until
reaction with moisture in the air began on the surface. Fur-
ther surface reaction, as observed under a microscope, oc-
curred at water droplets with little or no general surface cor-
rosion.
Light absorption by N a - in the solid is very efficient and
covers a broad spectral range extending throughout the visi-
ble and near infrared (cf. Fig. 8). If solids can be found in
which this absorption is followed by auto-ionization as in so-
lution126**], and if the lifetime of the conduction electron so
produced is long enough, sodium anions might be efficient
for photoelectric energy conversion. Because the electron is
only weakly bound to such anions as Cs- and may be even
more weakly bound in electride salts the photoelectric
properties of these substances would be most interesting. At
least in principle, such compounds have the potential to ex-
tend the wavelength of photoelectron emission farther into
the red than is possible with currently available photoemis-
sive surfaces.
Of course, such speculation about potential uses for al-
kalides and electrides is based upon very little fundamen-
tal information about their properties. Before more can be
done to utilize these compounds, a great deal of study is
needed to determine their properties. Measurements are not
easy with such reactive materials even when they can be pre-
pared in pure form. However, we hope that the demonstra-
tion that the - 1 oxidation state of the alkali metals is stable
will stimulate others to investigate such systems and find uses
for them.
The author is grateful to the National Science Foundation
for current support of this research under Grant No. DMR77-
22 975 and to the U.S. Department of Energy f o r prior support
under Contract No. EY-76-S-02.0958. Thanks are due to the
many graduate students and post-doctoral research associates
who worked on this project, most of whom may be identified as
co-authors of papers from this laboratory. Previously unpub-
591
lished wofk described in this paper was done by M. DaGue, H.
Lewis, P. Smith, B. VanEck and M . Yemen.
Received. August 9. 1978 [A 282 IEf
German version: Angew. Chem. 91, 613 (1979)
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