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CHAPTER 1
1.7
1.8
0.25
1.9
13.2 eV
1.10
Self-tests
1
0
S1.1
80
35 Br
S1.2
d orbitals, 5 orbitals
S1.3
S1.4
3p
S1.5
S1.6
Ni :[Ar]3d 8 4s 2 , Ni 2+ :[Ar]3d 8
S1.7
S1.8
S1.9
81
35 Br
1.11
1
1
7 1
= 1.0974 X10 m
2
1 2
= R
1
1
7 1
= 1.0288X10 m
2
2
1
= R
1 1
= 9.7547X106 m 1
12 32
= R
1 1
= 8.2305X106 m 1
12 22
= R
S1.10
1.12
0 up to n-X
S1.11
Cs+
1.13
n2
1.14
Exercises
1.1
(a)
14
7
N+ 42 He178 O+11p +
(b)
12
6
(c)
14
7
C+11p137 N +
1
0
3
1
12
6
N+ n H+ C
1.2
246
96
1
Cm+126 C257
112 Uub+ 0 n
1.3
1.5
9
4
1.6
9
4
12
6
ml
Orbital
designation
2p
3d
4
4
0
3
+1, 0,
1
+2, +1,
, 2
0
+3, +2,
, 3
Number
of
orbitals
3
4s
4f
1
7
1.15
1.16
Ne + He Mg + n
1.4
22
10
25
12
1
0
4
2
1
0
Be+ Be C+ He +2 n
2
1.18
1.19
1.20
1.21
1.22
(a) [He]2s22p2
1.30
(b) [He]2s22p5
(c) [Ar]4s2
(d) [Ar]3d10
(e) [Xe]4f145d106s26p3
(f) [Xe]4f145d106s2
1.23
(a) [Ar]3d14s2
CHAPTER 2
Self-tests
S2.1
(b) [Ar]3d2
(c) [Ar]3d5
(d) [Ar]3d4
(e) [Ar]3d
S2.2
(f) [Ar]
10
(g) [Ar]3d 4s
S2.3
Linear
S2.4
S22 : 1g22u23g21u42g4 ;
(h) [Xe]4f 7
1.24
(a) Angular
Cl2 : 1g22u23g21u42g44u1.
(a) Xe]4f145d46s2
S2.5
1g22u23g21u42g4
(b) [Kr]4d6
S2.6
[2-2+4+2] = 3
S2.7
S2.8
S2.9
21 kJ mol1
S2.10
(a) +1/2
(c) [Xe]4f
(d) [Xe]4f7
(e) [Ar]
(f) [Kr]4d
1.25
(a) S
(b) Sr
(b) +5
(c) V
(d) Tc
Exercises
(e) In
(f) Sm
2.1
(a) angular
1.26
(b) tetrahedral
1.27
(c) tetrahedral
1.28
1.29
2.2
2.3
(a) T-shaped
2.4
(b) one
(c) linear
(c) none
(a)
(d) two
2.15
(a) 1g22u2
(b) 1g22u21u2
Cl
Cl
(c) 1g22u21u43g1
I
Cl
Cl
(b)
(d) 1g22u23g21u42g3
2.16
2.17
(a) 1g22u23g21u42g4
(b) 1
S
1800
F
2.5
2.6
2.18
120 0
(a) 2
(b) 1
(c) 2
F
2.19
(a) +0.5
(a) tetrahedral
(b) 0.5
(b) octahedral
(c) +0.5
2.20
(a) 176 pm
(b) 217 pm
(c) 221 pm
2.7
2.8
2.9
483 kJ difference is smaller than expected
because bond energies are not accurate.
2.10
2.21
(a) 0
(a-c)
-1
2.12
(a) covalent
(b) ionic
(c) ionic
2.13
(a) sp2
(b) sp3
(c) sp3d or spd3
2 2
(d) p d or sp d.
2.14
(a) one
2.22
2.23
2.24
4
(b) electron precise
CHAPTER 3
Self-tests
3.4
3.5
XA2
K3C60
3.6
281 pm
3.7
429 pm
3.8
3.9
3.10
S3.1
S3.2
S3.3
52%
S3.4
rh = ((3/2)1/2 1) r = 0.225 r
S3.5
409 pm
3.11
S3.6
401 pm
3.12
S3.7
FeCr3
S3.8
X2A3.
3.13
S3.9
3.14
CsCl.
S3.10
LaInO3
3.15
S3.11
2421 kJ mol1
S3.12
Unlikely
3.16
S3.13
3.17
S3.14
NaClO4
S3.15
Schottky defects.
S3.16
S3.17
S3.18
(a) n-type
(b) p-type
Exercises
3.1
3.2
3.3
(b) CsCI
(a) MgSO4
(b) NaBF4
3.19
CsI < RbCl < LiF < CaO < NiO < AlN
3.20
3.21
3.22
3.23
3.24
3.27
Yes.
A semiconductor is a substance with an
electrical conductivity that decreases with
increasing temperature. It has a small,
measurable band gap. A semimetal is a solid
whose band structure has a zero density of
states and no measurable band gap.
Ag2S and CuBr: p-type; VO2: n-type.
CHAPTER 4
S4.9
S4.10
S4.11
Self-tests
S4.1
Exercises
4.1
S4.3
pH=1.85
S4.4
Which solvent?
dimethylsulfoxide (DMSO) and ammonia.
S4.5
S4.6
S4.7
4.2
of
the
(e) Si(OH)4?
SiO(OH)3.
bases
S4.8
(f) HS?
4.3
The
conjugate
base
is
acids
of
the
4.9
electron withdrawing
4.5
4.6
4.11
4.12
Kb = 5.6 10
10
4.14
Cl
H
O
chloric acid
chlorous acid
strong
to
be
4.16
studied
Cl
Ka = 5.6 106
4.7
4.17
4.26
2-Me-py or 4-Me-py?
4.27
4.25
2HCO 3-
4.28
NH2- + H2F+
4.30
H2SO4 + HF H3SO4+ + F-
4.24
<1
4.23
NH3 + HF
4-Me-py.
4.22
B(n-Bu)3.
[(H2O)4Fe(OH)2Fe(OH2)4+ + 2H3O+
Ca2+ +
Boron trichloride.
B(n-Bu)3 or B(t-Bu)3?
2[Fe(OH2)6]3+
CO 2 + CaCO 3 + H 2O
4.21
for
the
SiO2 + 6HF
2H2O + H2SiF6
or
SiO2 + 4HF
C6H5COOH + HF
2H2O + SiF4
(c) C6H5COOH?
4.37
4.38
4.39
acid-Cl- + I-
fH = -20.0kJ/mol
Al2 O 3 + 3H 2 S
Al2 S 3 + 3H 2 O
4.33
CHAPTER 5
Self-tests
S5.1
acid-I- + Cl-
4.36
(a) CH3CH2OH?
is:
CH 3CH 2OH + HF
3
HF
S5.3
S5.4
S5.5
S5.6
S5.7
S5.8
S5.9
S5.10
CH 3CH 2OH 2+ + F-
NH
NH
oxidation
3+
4.35
5 [ Zn(s) Zn2+(aq) + 2e ]
4.34
C6H5COO- + H2F+
F-
(e) Zn(s)?
Mn2+(aq)
S5.12
5.4
Exercises
5.1
Oxidation numbers?
2 NO(g) + O2(g) 2 NO2(g)
+1 -2
0
+4 -2
CaH2(s)
+2 -1
5.5
Standard potentials vary with
temperature in opposite directions? The
amino and cyano complexes must have
different equilibrium shifts with respect to
changes in temperature that results in the
opposite directions of change for the cell
potential.
5.6
10
5.13
5.14
Q = 1/(p(O2)[H+]4)
and
E = E [(0.059V)/4][log(1/(p(O2)[H+]4)]
(b) The reduction of Fe2O3(s)?
5.15
5.16
5.17
5.18
+ 6
2+
5.11
Base
5.19
5.20
5.21
5.22
5.23
5.24
CHAPTER 6
Self-tests
S6.1
S6.2
S6.4
S6.5
6.1
S6.7
S6.8
S6.10
S6.11
S6.12
S6.13
S6.6
S6.9
Analysis of the
S6.15
+T1u.
Exercises
Symmetry elements? (a) a C3 axis and a v
plane in the NH3 molecule?
N
H
H
H
C3
Cl
Pt
Cl
Cl
Cl
Cl
Cl
C4
6.2
Pt
Cl
S4 or i? (a) CO2? i
(b) C2H2? i.
(c) BF3? neither.
(d) SO42? three different S4.
6.3
Cl
12
6.4
6.5
6.12
6.15
6.8
6.9
px = (1/2)(1 2 + 3 3) (= T2)
py = (1/2)(1 2 3 + 3) (= T2)
pz = (1/2)(1 + 2 3 3) (= T2)
6.11
s = (1/2)(1 + 2 + 3 + 3) (= A1)
6.7
Exercises
CHAPTER 7
7.1
Self-tests
S7.1
CO
Ni
trans-diaquadichloroplatinum(II), trans[PtCl2(OH2)2].
OC
(b)
Diamminetetra(isothiocyanato)
chromate(III)?
[Cr(NCS)4(NH3)2] . ,can exist as, cis[Cr(NCS)4(NH3)2] or trans[Cr(NCS)4(NH3)2] .
(c) Tris(ethylenediamine)rhodium
[Rh(en)3]3+.
2-
NC
(III)?
Ni
NC
(d)
Bromopentacarbonylmanganese
(I)? [MnBr (CO)5].
CN
CN
(e) Chlorotris(triphenylphosphine)rhodium
(I)? [RhCl(PPh3)3].
S7.2
CO
CO
2-
Cl
Co
Cl
Cl
Cl
S7.3
(d) [Mn(NH3)6]2+?
Hexaamminemanganesium (II)
2+
S7.4
H3N
NH3
H3N
7.2
Mn
NH3
NH3
NH3
S7.5
(d) [Cr(NH3)5OHCr(NH3)5]Cl5
7.3
(c) [Co(C2O4)(en)2]+?
bis(ethylenediamine)oxalatocobalt(III).
14
7.4
M
L
square planar
tetrahedral
(b)
Isomers expected for MA2B2?
tetrahedral complex, no isomers, for a squareplanar complex, two isomers, cis and trans.
7.5
E
B
Trigonal Bipyramidal
A = axial ligands
A = axial
B = basal
E = equatorial ligands
7.6
[Mg(edta)(OH2)]2
7.11
7.12
[CoBrClI(OH2)]
7.13
7.8
7.9
7.10
Explain
the
difference
between
monodentate,
bidentate,
and
quadridentate? A monodentate ligand can
bond to a metal atom only at a single atom, a
bidentate ligand can bond through two atoms,
a quadridentate ligand can bond through four
atoms.
What type of isomers do you get with
ambidentate ligands? linkage isomers.
Which ligand could act like a chelating
ligand? (a) Triphenylphosphite, no/
(b) Bis(dimethyl)phosphino ethane (dmpe)
yes.
(c) Bipyridine (bipy), yes.
(d) Pyrazine, no.
Draw structures of complexes that contain
the ligands (a) en, (b) ox, (c) phen, and (d)
edta? .
A
A
E
B
M
C
B
D
E
C
A
E
D
E
S8.4
E
A
S8.3
7.16
A
C
A
E
S8.2
A
B
S8.5
A
B
E
S8.6
S8.7
Exercises
TiO2 in sunscreens?
Titania articles absorb this ultraviolet
radiation
Molecular shape and vibrational modes for
XeF2? Trigonal bipyramidal, 4 total
vibrational modes.
(a) 77Se-NMR spectrum consists of a triplet
of triplets? The triplet of triplets.
(b) Proton resonance of the hydrido ligand
consist of eight equal intensity lines? yes.
EPR signal of new material arises from W
sites?
Chiral (dien is
8.1
7.17
8.2
7.18
8.3
8.4
8.5
8.6
8.7
8.8
N
N
Ru
N
Ru
isomer
isomer
7.19
7.20
CHAPTER 8
Self-tests
S8.1
16
8.9
8.10
8.11
8.12
8.13
8.14
8.15
8.16
8.17
8.18
8.19
8.20
8.21
8.22
S9.1
S9.2
S9.3
S9.4
S9.5
Exercises
9.1
9.2
9.3
9.4
9.5
CHAPTER 9
Self-tests
10.3
9.7
9.8
9.9
H = 1, Re = +7.
CHAPTER 10
Self-tests
10.5
S10.1
(c)
Different
molecular
hydrides? Molecular hydrides are found in
groups 13/III through 17/VII.
GeH4
10.6
10.7
10.8
Exercises
(b) SiH4?
silane.
10.1
(c) NH3?
ammonia,
10.11
18
10.13
Most
likely
to
undergo
radical
reactions? (CH3)3SnH, the tin compound is
the most likely to undergo radical reactions
with alkyl halides.
10.14
CHAPTER 11
Self-tests
S11.1
S11.2
S11.3
10.16
10.17
M2CO3(s)
CO2(g)
2M+(g) + CO32(g)
O2(g) + CO2(g)
S11.5
of
methylbismuthine,
S11.6
10.20
The redistribution
BiH2Me.
2M+(g) +
M2O(s) +
Exercises
11.1
11.2
(b)
Why are group 1 metals poor
They are large,
complexing agents?
electropositive metals and have little tendency
to act as Lewis acids.
CHAPTER 12
S12.1
11.3
11.4
in
S12.2
S12.3
S12.4
11.7
11.8
11.9
Exercises
12.1
12.2
NaNH2
11.6
+ NH3
liquid
Self-tests
20
12.6
S13.2
MgSeO4
12.8
LiBH4 + NH4Cl
S13.3
Cl3BNCH3 + 3CH3MgBr
(CH3)3B3N3(CH3)3 + 3Mg(Br, Cl)2
S13.5
BH3NH3 + LiCl + H2
THF
11
S13.1
10
7, arachno species.
The structure of B4H10:
CHAPTER 13
Self-tests
[B10H11 (AlCH3)]
13
10
10
13.6
12
1,2 - B10C2H12
1,7-B10C2H12 (90%) + 1,12B10C2H12 (10%)
1,7-B10C2H10Li2
+
2Si(CH3)2Cl2
B10C2H10(Si(CH3)2 + 2LiCl
S13.8
1,7 -
13.7
13.8
Predict
the
products
from
the
hydroboration of (a) (CH3)2C=CH2, (b)
CH CH?
Exercises
13.1
13.2
13.3
13.4
13.9
BF3
13.11
(b)
13.12
C
(a) A = B2H6
(b) B = B(OH)3
heat
H2O
CaF2
LiAlH4
(a) BH3 +
(CH3)2C=CH2
B[CH2-CH(CH3)2]3
(b) BH3 +
CH
CH
B(CH=CH2)3
Diborane has been used as a rocket
propellant. Calculate the energy released
from 1.00 kg of diborane given the
following values of fH/kJ mol-1: B2H6 =
31, H2O = -242, B2O3 = -1264. The
combustion reaction is B2H6 (g) + 3 O2(g)
3 H2O (g) + B2O3 (s). What would be the
problem with diborane as a fuel?
-73,172 kJ.
(c) C = B2O3
Does B2H6 survive in air? If not, write the
equation for the reaction?
Heat, Ether
[HN(C2H5)3]Cl + NaBH4
H2 + H3BN(C2H5)3 + NaCl
22
+ C2H2
(2) B10H12(SEt2)2
B10C2H12 + 2SEt2 + H2
(3) 2 B10C2H12
+ 2EtO
+ 4EtOH
2 B9C2H12 + 2B(OEt)3 + 2H2
(4) Na[B9C2H12]
+
NaH
Na2[B9C2H11] + H2
THF
(5) 2Na2[B9C2H11] + FeCl2
2NaCl + Na2[Fe(B9C2H11)2]
2-
B
H
B
H
13.13
B6H10
13.14
13.15
13.16
(1) B10H14
+ 2SEt2
B10H12(SEt2)2 + H2
H
H
H
H
C
C
B
B
Fe
B H
B
B
B
H
H
B
H
B
H
13.18
Heat
(a) nido .
(b) 12.
(c) The total number of valence elections is
(10x3)+(14x1)=44; the number of cluster
valence is the remainder of 44-20=24.
13.17
B
H
B
B
B
C
Exercises
13.20
14.2
14.3
14.1
CHAPTER 14
Self-tests
S14.1
CH3
N
C
H3
S14.3
13
13
13
F
F
Si
CH3
H3C
F
F
(b) There are two different fluorine
environments.
14.4
Draw the structure and determine the
charge on the cyclic anion [Si4O12] ?
24
8-
14.11
Si
O
O
Si
Si
O
O
Si
Sn-NMR
14.6
Predict the appearance of the 1H-NMR
spectrum of Sn(CH3)4? Doublet
Charge = 8.
14.5
14.12
119
14.7
14.8
YYYYY14.9
(a) Summarize the trends in
relative stabilities of the oxidation states of
the elements of Group 14, and indicate the
elements that display the inert pair effect.
(b) With this information in mind, write
balanced chemical reactions or NR (for no
reaction) for the following combinations,
and explain how the answer fits the trends.
(i) Sn2+(aq) + PbO2(s) (excess) (air
excluded) (ii) Sn2+(aq) + O2(air) ?
(a) +4 is the most stable oxidation state for
the lighter elements, but +2 is the most stable
oxidation state of Pb. Pb therefore displays
the inert-pair effect.
(b) (i) Sn2+ + PbO2 + 4 H+ Sn4+ + Pb2+ +
2H2O, (ii) 2Sn2+ + O2 + 4H+ 2Sn4+ +
2H2O.
14.10
14.13
14.17
Exercises
15.1
P
As
Sb
Bi
O
S
Se
Te
Self-tests
S15.1
S15.2
S15.4
CHAPTER 15
15.2
Type of
element
Nonmetal
Nonmetal
nonmetal
metalloid
metalloid
nonmetal
nonmetal
nonmetal
nonmetal
Diatomic
gas?
yes
Inert pair
effect?
No
no
No
no
no
no
yes
no
no
no
No
No
Yes
No
No
No
No
Ca5(PO4)3OH + 5H2SO4
3H3PO4 (impure) + 5CaSO4 + H2O
(c) Account for the difference in cost?
26
2H3PO4(l) + 3CaCl2(aq)
Ca3(PO4)2(s) + 6HCl(aq)
15.9
(a) HNO3?
6Li + N2 2Li3N
High temperature
(b) NO2?
N2 + 3H2 2NH3
2NO2(aq) + 2OH(aq)
(d) N3?
3NaNH2(l) + NaNO3
15.5
at elevated temperatures:
15.10
P4 + 5O2 P4O10
(b) Reaction of the product from part (a)
with excess H2O?
as
oxidizing
or
E = 0.839 V.
LiAlH4
15.12
AS
Cl2
(a) A = AsCl3
(b) B = AsCl5
(c) C = AsR3
(d) D = AsH3
15.17
3RMgBr
Cl2/hv
tetrahedral.
15.18
15.15
(c) D = N2O4
(d) E= NO2
(e) F = NH4+
28
15.19
16.3
CHAPTER 16
16.5
16.6
In Presence of Cl
The
decomposition
is
of
H2O2
thermodynamically favored in presence of Cl
.
16.7
16.8
16.9
2+
O2
-0.13
1.51
HO2-
H2O2
16.10
16.11
S2O62and S2O32.
Use the standard potential data in
Resource section 3 to predict whether
SeO32 is more stable in acidic or basic
solution?
Exercises
16.1
The
decomposition
of
H2O2
is
thermodynamically favored in presence of Br
S16.2
Self-tests
S16.1
16.12
16.13
CHAPTER 17
Self-tests
S17.1
B
r2
liqu
id
lower
soft
er
I2
soli
d
lowest
soft
est
H
e
gas
N
e
A
r
K
r
X
e
gas
gas
gas
gas
gree
n
dark
redbro
wn
dark
viol
et
Col
orle
ss
colo
rless
colo
rless
colo
rless
colo
rless
2+
17.2
For F:
2 resonances.
S17.3
F2 + H2SO4 CaSO4 + 2 HF
2 HF + 2 KF 2 K+HF2
2 K+HF2 + electricity F2 + H2 + 2 KF
For Cl:
Exercises
17.1
Phy
sica
l
stat
e
Electron
egativit
y
gas
highest
(4.0)
C
l2
gas
lower
Har
dnes
s of
hali
de
ion
hard
est
soft
er
Col
or
2 X + Cl2 X2 + 2 Cl
I)
17.3
(X = Br,
light
yell
ow
yell
ow-
unwanted reaction:
2 OH(aq) + Cl2(aq) ClO(aq) +
Cl(aq) + H2O(l)
30
17.4
a).
b)
IF3:
X = IF4N(CH3)4
Different possible arrangements of
17.6
[ClF4] [SbF6] .
17.11
17.7
17.19
IF6+,
17.20
(a).
(b) I2O5?
17.15
17.21
17.22
17.17
.
Predict whether each of the following
compounds is likely to be dangerously
explosive in contact with BrF and explain
your answer: (a) SbF , (b) CH OH, (c) F ,
(d) S Cl ?
3
At pH 7, V = 0.788 V
17.23
Br3 + I2 2 IBr + Br
17.18
17.24
Periodic acid.
32
17.25
18.2
least
Argon.
expensive
inert
(c) XeO3?
18.4
Draw the Lewis structures of (a) XeOF4?
(b) XeO2F2? (c) XeO64?
CHAPTER 18
Self-tests
S18.1
Exercises
18.1
18.8
Identify the xenon compounds A, B, C, D,
and E?
A = XeF2(g)
B = [XeF]+[MeBF3]
C = XeF6
D = XeO3
E = XeF4 (g).
18.9
19.2
19.3
19.4
CHAPTER 19
Self-tests
S19.1
2 CrO42 + 3 MoO2(s) + 10 H+
+4; VO2
S19.2
S19.3
2+
Exercises
Without reference to a periodic table,
sketch the first series of the d block,
including the symbols of the elements.
Indicate those elements for which the
group oxidation number is common by C,
those for which the group oxidation
number can be reached but is a powerful
oxidizing agent by O, and those for which
2+
19.1
34
19.7
19.9
19.11
(c)
[Cu2(O2CCH3)4]?
242*2*4*2
configuration, no metalmetal bond in this
molecule.
19.12
19.13
O
O
O
Cr
Cr
O
19.14
S20.5
S20.6
S20.7
S20.8
S20.9
O
O
[Ru2Cl2(ClCO2)4]- :
2.5 +, mixed valence at the Ru center, in line
with the energy level scheme [0.5 (8-3)].
[Ru2 (CH3COCH3)2(ClCO2)4]: 2+, the bond
order of 2.0 should also be expected [0.5x(84)].
CHAPTER 20
Oh
1
D
are
are
Self-tests
S20.1
What is the LFSE for both high- and lowspin d7 configurations? A high-spin d7
configuration is t25geg2. High spin, 0.8 o.
S20.4
Exercises
20.1
36
(c) [Fe(CN)6]3? d5, low spin, one unpaired
electron. LFSE is 2.00.
(c) [Fe(CN)6]3
(d) [Cr(NH3)6]3+?
d3, three unpaired
electrons, low spin, LFSE = 1.20.
.20.7
20.8
20.9
20.10
20.4
20.5
(a) L = 0, S = 5/2? 6S
(b) L = 3, S = 3/2? 4F
(c) L = 2, S = 1/2? 2D
(d) L = 1, S = 1? 3P
20.11
(b) 3p2?
20.13
20.20
20.21
20.22
20.16
20.17
20.18
20.19
38
20.23
Exercises
21.1
21.2
21.3
21.4
CHAPTER 21
Self-tests
S21.1
S21.2
S21.3
2-
21.6
A
Pt(II)
complex
of
tetramethyldiethylenetriamine is attacked
by Cl- 105 times less rapidly than the
diethylenetriamine analogue. Explain this
observation in terms of an associative ratedetermining step. The greater steric
hindrance.
21.7
21.8
21.9
21.10
21.15
A two-step synthesis for cis- and trans[PtCl2(NO2) (NH3)] start with [PtCl4]2?
21.12
21.13
40
{[Co(N3)(NH3)5]2+,[V(OH2)6]2+} {[Co(N3)(NH3)5]+ ,
[V(OH2)6]3+}
21.19
3+
1 1
k = 1.41 10 dm mol s
CHAPTER 22
Self-tests
No.
S22.1
S22.2
S22.3
What
is
the
formal
name
of
[Ir(Br)2(CH3)(CO)(PPh3)2]?
Dibromocarbonylmethylbis(triphenylphosphine)iridium(III).
S22.4
S22.5
S22.6
Propose
a
synthesis
Mn(CO)4(PPh3)(COCH3) starting
[Mn2(CO)10], PPh3, Na and CH3I.
for
with
Mn2(CO)10 + 2 Na 2Na[Mn(CO)5]
Exercises
22.1
S22.8
S 22.9
(e) La(5-Cp*)3?
tris(pentamethylcyclopentadienyl)lanthanum(I
II), 18e;
(f) Fe(3-allyl)(CO)3Cl?
allyltricarbonylchloroiron(II), 18e;
(g) Fe(CO)4(PEt3)?
tetracarbonyltriethylphosphineiron(0);
(h) Rh(CO)2(Me)(PPh3)?
dicarbonylmethyltriphenylphosphinerhodium(
I),16e(i) Pd(Cl)(Me)(PPh3)2?
chloromethylbis(triphenylphosphine)
palladium(II), 16e;
(j) Co(5-C5H5)(4-C4Ph4)?
cyclopentadienyltetraphenylcylcobutadinecob
alt(I), 18e;
(k) [Fe(5-C5H5)(CO2)]?
dicarbonylcyclopentadienylferrate(0), 18e;
S22.11 Assess
the
relative
substitutional
reactivities of indenyl and fluorenyl (86)
compounds? Fluorenyl compounds are more
reactive than indenyl.
(l) Cr(6-C6H6)(6-C7H8)?
benzenecycloheptatrienechromium(0), 18e;
(m) Ta(5-C5H5)2Cl3?
trichlorobiscyclopentadineyltanatalum(V),
18e;
Cl
Ph3P
Cl
Cl
Ph
PPh3
Ph3P
(n) Ni(5-C5H5)NO?
cyclopentadineylnitrosylnickel(0),18e.
PPh3
Pd
Pd
PhCl
Cl
Cl
22.2
Sketch an 2 the interactions of 1,4butadiene with a metal atom and (b) do the
same for an 4 interaction.
22.3
42
with a single d-block metal atom such as
cobalt? (a) C2H4? 2
(b) Cyclopentadienyl? Can be 5, 3, or 1.
(c) C6H6? 6, 4, and 2.
22.8
Provide plausible reasons for the
differences in IR wavenumbers between each of the
following pairs:
(a) Mo(PF3)3(CO)3 2040, 1991 cm1 versus
Mo(PMe3)3(CO)3 1945, 1851 cm1? CO
bands of the trimethylphosphine complex are
100 cm1 or more lower in frequency. PMe3 is
primarily a -donor ligand. PF3 is primarily
a -acid ligand.
(b) MnCp(CO)3 2023, 1939 cm1 vs.
MnCp*(CO)3 2017, 1928 cm1? CO bands
of the Cp* complex are lower in frequency
than the corresponding bands of the Cp
complex. Cp* is a stronger donor ligand than
Cp.
22.9
22.5
22.10
22.11
22.13
22.14
22.15
22.17
CO
CO
CO
1
22.16
W CO
CO C:
B:
3
-2 C O
-C O
-H
Fe
OC
Fe
CO
CO
OC
H
CO
[-C5H5Fe(CO)2]2
C
W CO
CO
CO
When
Fe(CO)5
is
refluxed
with
cyclopentadiene compound A is formed
which has the empirical formula C8H6O3Fe
and a complicated 1H NMR spectrum.
Compound A readily loses CO to give
compound B with two 1H-NMR resonances,
one at negative chemical shift (relative
intensity one) and one at around 5ppm
(relative intensity 5). Subsequent heating of
B results in the loss of H2 and the
formation of compound C. Compound C
has a single 1H-NMR resonance and the
empirical formula C7H5O2Fe. Compounds
A, B, and C all have 18 valence electrons:
identify them and explain the observed
spectroscopic data.
+ F e (C O ) 5
+
A:
D = C5H5Mo(CO)3. E = C5H5Mo(CO)3Br.
F = C5H5Mo(CO)3Na.
22.20
44
22.21
(a)
Fe(5 C5H5)2 + CH3COCl
5
Fe( C5H5)(5 C5H4COCH3) + HCl
22.27
(b)
Cl
Fe
22.22
22.23
22.24
O
Cl
A lC l 3
C H 2C l2
Cl
Fe
H 2 O , t-B u O K
DME
C O 2H
Fe
CHAPTER 23
Self-tests
S23.1
S23.2
S23.3
22.26
(PR3)2
A -hydrogen
Exercises
23.1
23.10
23.11
23.3
CHAPTER 24
S24.1
S24.2
S24.3
23.4
23.5
23.6
23.7
23.8
23.9
Self-tests
Exercises
24.1
24.2
24.3
24.4
24.5
24.6
46
24.7
24.8
Antiferromagnet ordering?
In an
antiferromagnetic substance, the spins on
different metal centers are coupled into an
antiparallel alignment. As the temperature
approaches 0 K, the net magnetic moment
goes to zero.
24.9
24.10
24.11
24.12
24.13
24.14
24.15
24.16
Oxotetrahedral species in
structures? Be, Ga, Zn, and P.
24.17
24.18
24.19
24.22
CHAPTER 25
Self-tests
S25.1
S25.2
S25.3
Exercises
25.1
25.2
Electron
length
and
quantum
confinement? A characteristic length is the
exciton Bohr radius.
25.3
25.4
25.5
(a) Top-down versus bottom-up? The topdown approach requires one to carve out
nanoscale features from a larger object. The
bottom-up approach requires one to build
up nanoscale features from smaller entities.
(b) Advangtages and disadvantages? Topdown methods allow for precise control over
the spatial relationships. Bottom-up methods
framework
24.21
25.7
25.8
25.9
Vapor-phase
versus
solution-based
techniques? (a) Vapor-phase, large sizes. (b)
Vapor-phase, more agglomeration.
25.10
25.11
25.12
25.13
25.14
25.15
25.16
25.17
25.18
Shell
Core
48
25.19
25.20
25.21
25.22
25.23
25.24.
25.25
S26.4
Exercises
26.1
CHAPTER 26
26.4
Self-tests
S26.1
Bionanocomposites
and
improved
mechanical strength? Biomimetics need
trabecular and cortical bone tissues, which
combine compressibility and tensile strength.
Hybrid alumoxane nanoparticles dispersed in
PPF/PPF-DA shows enhanced strength.
D,L
S26.2
S26.3
26.5
26.7
26.8
26.9
26.10
26.11
26.15
CHAPTER 27
Self-tests
S27.1
S27.2
S27.3
S27.4
S27.5
S27.6
S27.7
S27.9
26.12
26.13
S27.8
50
Exercises
27.1
27.2
27.3
27.4
27.5
27.6
27.7