Carlos A. L.

Filgueiras and Fernando Carazza Universidade Federal de Minas Gerais 30000 Belo Horizonte-MG Brasil

I
I

Electronic Transitions as a Probe of Tetrahedral Versus Octahedral Coordination in Nickel(l1) Complexes

An undergraduate inorganic chemistry experiment
Electronic Spectroscopy Figur? 1 show the spertra uf the fotrr-coordinate complex in ni~rumethnne acetonitr~le, of the six-c<x,rd~narrcomplex 107 nnd 2nd in ammonia solution. The latter is insoluble in most usual solvents. The spectra were taken in a Beckman DB-GT speetrophotometer using 1.0 cm path length cells. Transitions observed in the spectra: Species Absorptions em-' nm
6

T h e preparation of metal ion complexes with the same ion and different symmetries and the study of their electronic spectra can illustrate many different aspects of ligand field theory. If those complexes belong t o the two most important geometries, the tetrahedral and the octahedral cases, their study can be even more interesting and illustrative, especially if t h e experiments can he performed by the students themselves a t a n introductorv course on coordination chemistrv. Here we present such a scheme, involving t h e preparation of a tetrahedral nickel(I1) c o m ~ l e x its transformation into and a n octahedral speciks,' followed by a discussion of spectral results.
~~ ~~

(I m-I cm-')

Experimental
Tetrahedral Nickel(l4 Complex: (BudN)21~ i B r 4 I Four-coordinate tetrahedral complexes of Ni(I1) are best prepared as anions of large cations in non-aqueous media ( 1 ) . The starting materials chosen were tetrahutvlammonium bromide and nickel(I1) bromide. Anhydrous NiBrn was prepared by the reaction NiC03.2Ni(OH)s. 4H20 + 6HBr 3NiBrz + 9Hz0 + COa The reaction is very easy to perform and gives a yellow powder of NiBrzupon heating to drynessat 150C. The yield is high (96%),and the product must be stored in a desiccator. he synthesis of bis(tetrabutylammonium)tetrabromonickelate(Il) was similar to that of (EbN)21NiCIIIdescribed in InorganicSyntheses (2). The reaction wascarried out inahsoluteethanol and thesolvent evaporated to almost complete dryness. Addition of carbon tetrachloride caused the precipitation of the blue hygroscopic complex. The excess ammonium salt dissolved in carbon tetrachloride and iiltratlonc,t'thc mixturegave the purr rumplex. 0.271 g (1.25 X 10-' mdei, of NiBr, and twice that numher of malrr of HurNHr yielded 0.XY y of I B U ~ N I NiHr41.ur71'".
~ ~ ~~ ~

ammonia wlution

-.

580

17.241

6.7

Octahedral Nickel(l0 Complex: ( Ni(NH&( Br2 Hexaaminenickel(I1)hrornide was prepared by the reaction of the four-coordinate complex described above with a slight excess of concentrated ammonium hydroxide. Immediate precipitation of a bluish-purple powder occurred, which was made complete by the addition of ammonium chloride. The precipitate was filtered and kept in a desiccator. The product was identical with that obtained by the direct reaction between NiBra and NH3. Starting with 0.501 g (5.80 X moles) of ( B U ~ N ) ~ I N the yield~ 0.129 g (69%). ~ B ~ & was

Theoretical Considerations NiUI), with a d8 configuration, is an 3Fspecies in the ground state. For a n octahedral Ni(I1) complex one should expect a situation such a s t h a t of the diagram in Figure 2 for the split 3F term and t h e higher lying unsplit 3Pterms (3). T h e 3T1g(F) and 3TM(P)terms, having the same symmetry, will mix t o some extent, lowering the energy of the 3Tlg(F) state a n d raising t h a t of the 3 T y ( P ) state. Keeping in mind the fact t h a t t h e tetrahedral splitting corresponds t o a n inverted octahedral case, one can draw a qualitative Orgel diagram for the two symmetries, such a s shown in Figure 3.

,.

rm

roo

eoo

rm

m0.m

3 m

.m

roo

.oo

. m

Figure 1. Electronic spectra o [NiBrr12- and [Ni(NH3)8]Z+. f

826 1 Journal of Chemical Education

Figure 2. Spllning of terms for a de species in an Ohfield.

The six-coordinate INi(NH&I 2+ complex shows only two absorptions, both with values close to 10 1m-' cm-'. This is indicative of a spin allowed, Laporte forbidden transition, that is, a centrosymmetric complex with Oh symmetry. Oh complexes of Ni(I1) are expected to exhibit three ahsorptions, however (4):

3~zB%3~u(~) The Racah parameter B' for Ni(I1) in INi(NH&I2+ can be calculated ( ) giving avalue of 857 cm-I. Using the absorption 5. energies obtained from the spectrum of INi(NHd6!2+, one gets EIB' values of 32.2 and 20.1. These results taken rnto the Tanabe-Sugano diagram f o a ds species (6) ~ show that the two The Tanahsor~tions corres~ond us and u?. res~ectivelv. to -. . ahe-Sugano diagram further shows that u, corresponds to an EIB' ratio of 12.4. or to an ahsorption value of 10.627 cm-I (941 nm), in the near infrared portion of the spectrum. The Tanabe-Sugano diagram also gives the ratio DqlB' = 1.22, from which one gets Dq = 1046 cm-I. If one compares this with the Dq value estimated from JQrgensen's equation (7) Dq(kK) 880x1 fiwd =
~ ~~~

Fisve 3. hgel s g m fa hOn and 6 splltWw ot a @species. The subsdm aa g daes not apply to lhe left-hand si6e o lhe tlgure since a Td species Ma no f
center o f

symmetry.

All possihle transitions derived from Figure 3 are spin-allowed, since the spin multiplicity remains constant. The Laporte selection rule, however, forbids such g-g transitions between two d orbitals. This rule can he partially overcome by two mechanisms:
(1) by d-p mixing between d and p orbitals in the complex, which can occur if the bonding orbitals of the metal have nog or u character
(2) by a vibronic type ofmechanism in which coupling hetween the vibrarimal and electronic components of the wavefunction in an uniymmetrical configuration of an otherwise symmetrical molecule (in the absence of vibrational motion) confers upon the electronic transitions a certain g u character
(TA ,."ra.c\:

10

Comparing the two mechanisms described one sees that the former is more effective, being operative in complexes without a center of symmetry, whereas the latter presupposes a temporary destruction of such a center due to unsymmetricalvihrations. Therefore one can expect more intense transitions in the first case, i.e., higher values of E in the Td case as compared t o the Oh case.
Discussion of Results The intense multiple band shown by I N ~ B I ~ I centered -~, between 14,000 em-' and 15,000 cm-', is characteristic of tetrahedral Ni(I1) complexes (3). Since this is an absorption a t the low energy end of the visible spectrum, the complex is blue. The values of r (of the order of 102 1m-I em-') are indicative of a Td species devoid of a center of symmetry and thus likely to show d - p mixing, with a partiallifting i f the Laporte selection rule. The possible transitions are (3)

in which g = 8.7 and f = 1.25, one ends up with D q = 1088 cm-1, which is in reasonable agreement with the TanabeSugano result. Although it is difficult to estimate the D q value of the tetrahedral complex one must hear in mind that its highest energy absorption (us) lies a t the end of the visible region, whereas for the octahedral complex the highest energy ahsorption lies in the ultraviolet and of the other two ahsorptions one is ohserved in the visihle region and the other is expected in the near infrared. This is due to ammonia being a hetter ligand than the hromide ion and to higher Ilq values for uctahedral versus tetrahedral coordination (not considering solvation effects).
Conclusion

The electronic spectra of Ni(I1) complexes illustrate the dramatic changes one observes on going from a four-coordinate (tetrahedral) to a six-coordinate (octahedral) species. A tetrshedral complex will show lower absorption energies, due t o its lower Dg value, as compared to an octahedral complex. ~nrthermore,'thespectra will also show that molar absorptivities are much higher for the Td species (spin-allowed, Laporte allowed via d-p mixing) than for Oh species (spinallowed, Laporte forbidden). Thus fundamental aspects of coordination chemistry can he demonstrated hy simple experiments that can be performed a t an introductory level course.
Literature Cited
(I) G ~ U , s., and N Y ~ O R.s.,J. them. Sm., 1873(1959). N. ~ , (2) Gill, N. S..andTaylor,B. R.,Inorganic Synfheaoa.9.136 (1961).

3T1s

%TI ~TI(P) 3

(3) Cottao,B.A, and WilLioson.G.. "Advanced Inorganic Chemhhy," 3rd Ed., Interscirneo, New York. 1972,pp.513-577. (I)Nichols, D., "Camplore8 and Firat-Row Trmition Elemmnte,'' MaeMillan, London.

in the only the third (v3) is Of the transitions visible spectrum of tetrahalonickel(I1) complexes (3). The first two transitions, vl and vz, fall in the infrared part of the spectrum and were not observed in any of the solvents used.

(5) Dmgo, R S..ThysicalMethds Chemiltw,''Saunders, Phihdelphh lW7.p. 38% in (6) ~ u hJ. E . ,~Y ,, , ~ ~~ i ,c ~ l a w - - ~ & t it~ i ~ ~ ~paetivit~," ~ ~~ ~ ~ f s r vand~ ~ d name, &Ron,1972,pp.364-365.

1974,~. 95.

g$:L,
196%

C.

K ,,GOlidation .

and Oxidation

Stam,"Sp-r,

Nw York,

Volum 57, Number 11, November 1980 / 827