Vibrational spectral study of ZrCl4 and HfCl4 complexes with

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Jan 20, 1981 - Abstract-The. Raman and i.r. spectral data of the addition compounds of ZrCI, and HICI, with acetonitrile and acetonitrile-dx have been ...
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Vol. 37A. No. 9. pp. 71 l-719, 1981.

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Vibrational spectral study of ZrCL and HfCL complexes with acetonitrile and acetonitrile4 YOSHIYUKI HASE and OSWALDO L. ALVES Instituto de Quimica, Universidade Estadual de Campinas, C.P. 1170, 13100 Campinas, SP, Brasil (Received

20 January

1981)

Abstract-The Raman and i.r. spectral data of the addition compounds of ZrCI, and HICI, with acetonitrile and acetonitrile-dx have been investigated for the polycrystalline samples. A detailed vibrational assignment of the observed bands above 2OOcm-’ has suggested to these complexes a cis-configuration with two non-equivalent ligands. The normal coordinate calculations have been performed using modified Urey-Bradley force field to obtain the force constants and potential energy distribution.

INTRODUCTION

The CrN bond stretching vibration for acetonitrile molecule is known to be in Fermi resonance with the combination band between the CH, symmetric bending and C-C stretching vibrations and this Fermi interaction is, of course, absent in acetonitrile-&[1,2]. In spite of the characteristic fundamental band shifts due to coordination effects, the CH3CN complexes showed also a Fermi resonating satellite band, which may be attributed to the above combination, to the side of the CrN stretching band[3-101. In the cases of the addition compounds with Tic& and SnC14[7], a new CEN band splitting of about 5 cm-’ was found for both the CHXN and CDXN complexes. A slight ligand fundamental band splitting was further observed for the C-C stretching and CCN linear bending vibrations. On the other hand, only two characteristic bands due to Fermi resonance of about 25 cm-’ were found in the CzN stretching band region of the addition compounds of CH,CN with BF,, BCl,, BBr,, SbFS, SbCI,, NbQ, TaC&, ZnCl,, ZnBr, and ZnI,[3-6,8-101. In the present study, the vibrational analyses are investigated on the Raman and i.r. spectral data found for ZrC1,.2CD,CN, ZrCl.+.2CH,CN, HfC14.2CH,CN and HfC14.2CD3CN and the normal coordinate calculations are performed using the modified Urey-Bradley force field. The molecular structure is discussed by comparing the vibrational spectral data with the selection rules. EXPERIMENTAL The investigated compounds were prepared according to the method described in the literatureIll] and the purities were examined by elemental analyses for Zr, Hf and Cl. The Raman spectra were obtained in the region from 4000 to IOcm- with a Cary 82 spectrometer equipped with an argon ion laser in which the 488.0 and 514.5 nm lines were used for excitation. The samples were in the form of polycrystalline powder in capillary cells. SAA Vol. 37A. No. 9-A

The i.r. spectra of the polycrystalline samples were recorded in the 4000-180cm-’ region for nujol and fluorolube mulls between two CsI or polyethylene plates, on a Perkin-Elmer IR 180 spectrophotometer. All sample manipulations were carried out in a dry box.

RESULTSAND DISCUSSION

The vibrational spectral data experimentally observed for ZrCl+2CHaCN and ZrC1+2CD,CN with the aid of Raman and i.r. spectroscopy are summarized in Table 1, together with the band assignment, and those for HfC14.2CH,CN and HfC14.2CDSCN in Table 2. An octahedral coordination compound of the formula MC&L2 exhibits cis-trans isomerism. Since the truns-isomer possesses a center of inversion on the central metal atom and belongs to DAh point group on a point mass assumption for the methyl groups, the Raman-i.r. mutual exclusion rule is expected to be effective. On the other hand, the &-isomer belongs to C,, point group which gives the coincident Raman and i.r. bands for most of the fundamentals and the ligand vibrations may show band splittings in this force field. To facilitate the vibrational analyses, the band assignment is carried out separately to the ligand vibrations and to the skeletal vibrations. Among the ligand fundamentals, the CH, stretching, bending and rocking bands are considerably affected by deuteration. Indeed, the bands observed at about 2995,2930,1395,1355 and 1020cm-’ are attributable to the CH, fundamentals and the corresponding CD3 bands are found at about 2225,2105, 1020, 1090 and 843 cm-‘, respectively. This band assignment can be supported by comparing with that for free CH,CN and CD,CN[l, 21. To explain the irregular isotope effect on the CH, and CD, symmetric bending bands, a mechanical coupling between the CD, symmetric bending and C-C stretching modes must be taken into consideration. This mode mix711

Y. HASE and 0. L. ALVES

712 Table

1. Vibrational

spectral

data (cm-‘)

for ZrCl,.2CH$ZN and ZrC1,.2CD&N

ZrCl4.2CD3CN

ZrClq.2CH3CN

Assignment

I. r.

Raman

Raman

1.r.

2997 w

2994 w

CH3

asym.

2933

2933 w,sh

CH3

sym.

5

2920“3 2312

s

2305

s

2928

s

2313 2306

5 s

s

2277

s

2286 2278

1393 m

1358 In

1360

m

1356 m

1356

5

VW

412 w

1022

s

947 937

5

405 w 396

395 m

CSN

stretch asym.

2107 s 2104 5

2108 2104

s s

CD3

sym.

CHj

asym.

CH3

sym.

bend

CDg

sym.

bend

CH3

rock

1093

VW

1018 m

asym. stretch

C-C

stretch

844

m

CD3

rock

CCN

bend

CCN

bend

383 w,sh 378 w,sh

357 S

352

vs,br

337 w

Zr-Cl'

asym.stretch

Zr-Cl'

sym.

zr-CI"

asym.

Zr-cl"

sym.

314 w 238

242 w

236 w

236 w

Zr-N

sym.

214

Zr-N

asym.

220 VW

215 VW 179 VW

145 m

145 m

121 s

121 S

96 m,br

97 m,br

67

67 VW

VW

52 w

S

VW

stretch stretch stretch

stretch stretch

185 m

196 m VW

bend

s s

311

180

bend

CD3

314 w

VW

stretch

C-C

312 s

220

stretch

857 851

375 w 353 vs,br

336 w

w

(Fr)

CD3

m m

375 w s

stretch

m m

385 w,sh 380 w

357

C%N

5

411 402

w

s

2249 2200

1020 VW 948 w 937w

s

2293

(Fr)

2249 m 2200 m

1093 w 1020

2301

5 s

1397 w

stretch

combination

2300 s 2292 “S 2284

stretch

ZrCl,,N? bend

ZrNC

bend

53 w

38 5

39 S

24 s

24 s

16 s

16 s

lattice

vibrations

The following abbreviations have been used: s, strong; m, medium; w, weak; v, very; br, broad; sh, shoulder; Fr, Fermi resonance. ing results also a slight isotope wavenumber shift on the C-C stretching band. The observed band position is about 94Ocm-’ for the CH,CN complexes and about 855cm-’ for the CD,C!N complexes. On the other hand, the CCN linear bending is mechanically coupled with the CDS rocking mode and the fundamental band at about 400 cm-’ is shifted to about 380 cm-’ upon deuteration. The CnN stretching band is undoubtedly found at about 23OOcm-’ for the CD&N complexes, while that for the CH3CN complexes is in Fermi

resonance with the combination between the CH, symmetric bending and C-C stretching modes. The resulting bands are found at about 2310 and 2280cm-‘. The Fermi resonance corrected C=N bond stretching wavenumbers are quite comparable with the fundamental wavenumbers observed on the CD,CN complexes. As easily seen in Tables 1 and 2, the most of the ligand fundamentals give slight band splittings due to intramolecular or intermolecular interaction between two ligand molecules or due to two non-equivalent ligand molecules. Taking into

Study of ZrCld and HfC1, complexes with acetonitrile and acetonitrile-d3

71:

Table 2. Vibrational spectral data (cm-‘) for HfCIe2CH3CN and HfC1,.2CQCN HfCl4.2CH3CN

HfCl4.2CD3CN Assignment

Raman

I.r.

Raman

2998 w

2996 w

2933 5

2933 s

2928

ys

29285

2314

s

2307

s

2315 2307

5 s

5

2279

s

2287 2280

f vs

VW

1398 m

1358

m

1359

5

1356 m

1355

5

VW

1021

s

943 940

s 5

415 w 408 m

413 m 405 m

398

396 m

VW

s

" m

2248

m

2197

m

2107 2103

s s

2108 2104

5 s

1020 351 w 342 w

s

2295

2249 2198

1030 w 1020

2302

5 s

1398

CH3

asym.

CH3

sym.

stretch stretch

combination 2304 2235

2285

1.r.

VW

lo89

VW

lole m

::z

m

a57 851

842

VW

844 m,sh

385 w,sh 375 w

s 5

384 w 373 w

(Fr)

CcN

stretch

EN

stretch

CO3

asym.

CO3

sym.

CH3

asym.

(FF) stretch

stretch bend

CHx

sym.

bend

CD3

sym.

bend

CH3

rock

CD3

asym.

C-C

stretch

bend

C-C

stretch

CD3

rock

CCN

bend

CCN

bend

363

VW

351

s

j51

vs

350

s

350

vs,br

Hf-Cl'

asym.stretch sym.stretch

330

w,sh

w,sh

Hf-Cl'

365 VW

332

vs,br

330

330 vs,br

Hf-Cl"

asym.

310 w

310

vs,br

311 w

310

Hf-Cl"

sym.

233

VW

241

w

238

VW

235 w

Hf-N

sym.

221

VW

223

VW

220

VW

219 w

Hf-N

asym.

203

m

stretch stretch

stretch stretch

194 m

130 VW

lea VW

142 m

144 m

125 s

125 s

101 m,br

102 m,br

70 WJ

70 VW

52 w

54 w

37 s

37 5

21 5

21 s

14 s

14 s

For abbreviations,

"S

HfCl,,Na bend

HfNC

bend

lattice

vibrations

see footnote to Table I.

account the vibrational spectral data for the zinc halide complexes with CH,CN and CD,CN[8,9], the latter term seems to be more reasonable to explain the band separations of about 5cm-‘. The symmetry lowering of the ligand by coordination can not be accepted as the first factor because the non-degenerate fundamentals of ligand vibration also show the band splittings. The typical band splitting in the CEN stretching region is illustrated in Fig. 1. According to the selection rules derived on MC&L, skeletal vibrations, two Raman and one i.r.

active M-Cl stretching fundamentals are expected for the trnns-isomer, while the &-isomer should have four M-Cl stretching fundamentals active in both the Raman and i.r. spectra. A recent study for TiCl+2CH,CN, TiC14.2CD3CN, SnC14.2CH3CN and SnC1+2CD,CN showed that the M-Cl stretching bands for these complexes were easily distinguished from other skeletal vibrations and were found in the same wavenumber region with those for MCI, and MC&‘[7]. Consequently, taking into account the fundamentals for ZrC14, ZrCl;‘, HfC& and HfCl;z[12-15], the Zr-Cl and Hf-Cl stretching

Y. HASE and 0. L. ALVES

714

2310

2270cm-' 2310 I

2270 I

I

2310

I

I

2270

I

~

-(b)-

I

I

2310

I

I

1

2270

2310

-(c)--

I

I

b I

2270

cm-1

Fig. 1. The Raman

and i.r. spectra

-kO--

2310

in the region

2270

I

2310

of the C=N stretching

I

2270

vibration

for (a)

ZrC14.2CHSCN,(b) ZrCl,.2CD,CN, (c) HfCI,.ZCH,CN and (d) HfCl+2CD,CN. bands of the investigating complexes are expected in the 410-240cm-’ and 390-260 cm-’ regions, respectively. As seen in Tables 1 and 2 and also in Fig. 2, the four bands of the ZrCl, complexes at about 375, 355,336 and 312 cm-’ are attributable to the Zr-Cl stretching modes and the four bands of the HfCl., complexes at about 364, 350, 330 and 310cm-’ to the Hf-Cl stretching ones. The fact that four M-Cl stretching bands are found for each complex results a &-configuration for ZrC14.2CH&N, ZrCl.,.2CD,CN, HfCL2CHXN and HfC1.+2CD,CN. The molecular structure is given in Fig. 3. Since the i.r. intense bands at about 312 and 310cm-’ are found to be less sensitive to the central metal elements, these can be assigned to the M-Cl” symmetric stretching mode. The bands at about 355 and 350cm-’ are assigned to the M-Cl’ symmetric stretching mode because of their Raman intensities. On the other hand, the bands at about 375 and 336cm-’ and at about 364 and 330 cm-’ are assigned to the M-Cl’ and M-Cl” asymmetric stretching modes by considering the Pans-influence by CH,CN/CD,CN and Clligands. From the vibrational spectral data previously reported for the metal halide complexes with CH3CN and CDsCN[5-101, the M-N stretching

bands should be weak in both the Raman and i.r. spectra and expected in the 2OOcm-’ region. Therefore, the bands at about 240 and 220 cm-’ are reasonably assigned to the symmetric and asymmetric stretching modes, respectively. The skeletal bending and MNC linear bending bands are found in the region below 220cm-’ and are assigned rather tentatively by comparing with the corresponding fundamental bands of the TiCI., and SnCI, complexes[7] and by taking the results of the normal coordinate calculations into consideration. Below 90cm-‘, there are five Raman bands for each complex. The observed wavenumbers are about 67,52,38,24 and 16 cm-’ for,ZrCl,.2CHXN and ZrC14.2CD3CN and about 70, 53, 37, 21 and 14 cm-’ for HfC1.+2CH,CN and HfCL2CDJJN. Since no bands show characteristic wavenumber shifts upon deuteration, these bands are attributed to the fundamental and combination modes of the lattice vibrations.

NORMAL COORDINATE

ANALYSIS

The normal coordinate calculations were performed on the basis of &-configuration by application of Wilson’s GF matrix method 1161. In the

Study of ZrCL and HfCh complexes with acetonitrile and acetonitrile-d, 360 I

I

320 I

366 I

320 lrn-' 360 I

1

I60

320

320

I

I

I

360 I

I

;‘,. L -09

t

I

-

I

320 I

-_(d)-

1

1

360

I

I

I

320

360

8

Fig. 2. The Raman and i.r. spectra in the region of the M-Cl stretching ZrCl,.2CH,CN,

715

(b) ZrCl,.2CDJ!N,

I

320

vibration (c) HfC&.2CH&N and (d) HfC&.2CD$N.

Fig. 3. The structure of MCl,.2CXpCN (M = Zr and Hf; X=HandD).

absence of structural data, the molecular parameters were assumed to be the same as for SnC1,.2CH3CN[17], except for r(Zr-N) = r(HfN) = 2.33 A and r(Zr-Cl) = r(Hf-Cl) = 2.34 A. A modified Urey-Bradley force field with two stretch-stretch truns-interaction force constants, I(M-N, M-Cl’) and I(M-Cl”, M-Cl”), was assumed in this study and the defined force constants were refined by the least squares procedure[lS, 191 to reproduce the observed fundamental wavenumbers.

for (a)

The numerical calculations were carried out for the internal symmetry coordinates, whose numbering and approximate description are summarized in Table 3, with a set of computer programs [20], using an electronic computer PDP10 at the Centro de Computacao Eletronica of the Universidade Estadual de Campinas. The final set of force constants listed in Table 4 gives satisfactory agreements between the observed and calculated fundamental wavenumbers and the calculated potential energy distribution gave support, as a whole, to the vibrational band assignment. The calculated wavenumbers and potential energy distribution for ZrC1.,.2CH,CN and ZrC14.2CD3CN are listed in Table 5 and those for HfC14.2CH3CN and HfC14.2CD3CN in Table 6. According to the donor-number defined by Gutmann[21], the basicity of acetonitrile as a solvent is found to be weak in spite of its high polarity. The metal-ligand force constants obtained, K(Zr-N) = 0.890 mdynlk’ and K(HfN) = 0.961 mdyn/k’, are comparable with K(TiN) = 0.794 mdyn/A-’ and K(Sn-N) = 0.668 mdyn/& [7] and these values seem to be reasonable to the coordination bonds[22]. From the results, it is found that the order of increasing

Y. HASE and 0. L. ALVES

716 Table 3. Approximate

CHs/CDs

asymmetric

CH3/CD3

symmetric

C-N

and numbering for symmetry coordinates

stretch stretch

al

a2

bl

b2

Sl

516

526

535 536

S2

stretch

537

S3

CH3/CD3

asymmetric

CH3/CD3

symmetric

CH3/CD3

rock

C-C

description

bend

S4

bend

bend

stretch

s9

M-Cl"

stretch

SIO

S6

stretch

CH3/CD3

bend

skeletal

bend

bend

internal

543 s30 SW!

s13.s14

s22

s31

s451s46

515,516

$23

532

s47

s17

524

533

548

s25

534

rotation

Table 4. Urey-Bradley

542

512

bend

skeletal linear

s29

Sll

skeletal

M-NSC

s21

S40 S41

M-Cl'

Cl-M-Cl

S28

s7

linear

N-M-Cl

SZO

536 $39

s6

stretch

N-H-N

527

55

C-CEN

M-N

s19

force constants (mdyn A-‘) ZrCl4.2CH3CN

HfCl4.2CH3CN

ZrCl4.2CD3CN

HfCl4.2CD3CN

K(M-Cl')

1.726

K(H-Cl")

1.427

1.564

K(H-N)

0.890

0.961

K(ClN)

17.975

17.951

K(C-C)

3.941

3.944

K(C-H/C-D)

4.469

4.465

H(NMN)

0.004

0.003

F(N..N)

D.ZOOt

0.200t

H(NMCI)

0.035

0.054

F(N..Cl)

D.ZOOt

D.ZODt

H(CIMCI)

0.094

0.107

F(CI..Cl)

0.100t

0.1oot

H(CCH/CCD)

0.189

0.183

F(C..H/C..D)

0.618

0.635

H(HCH/D~D)

0.386

0.389

F(H..H/D..D)

0.060

0.057

H(CCN)

D.lOl*

0.103*

H(HNC)

0.101*

0.103*

I (N-N,M-cl')

0.009

0.046

I (H-CI",M-Cl")

0.249

0.104

1.980

*Assumed to be HKCN) = H(MNC). tFrom reference [7]. covalent character is Sn-N < Ti-N < Zr-N < HfN and is contrary with that of increasing electronegativity of the central metal. This fact is explicable by considering the effective positive charge on the metal atom in the MCI, moiety. The weak M-N bond also reflects directly on the values of H(NMN), H(NMCI) and I(M-N. M-W. Since the M-Cl bond of the MCI, complex may be expected, on the basis of electron distribution, to be weaker than that for MCI, free molecule and stronger than that for MCl;’ complex ion, the

M-Cl force constant for the complex molecule should be between the values for MC& and MCI;* as already found for the TiCL and SnCX complexes[7]. Indeed, K(Zr-Cl) = 1.726 and 1.427 mdyn A-’ are smaller than 2.296 mdyn A-’ for ZrCl,[lZ] and larger than 1.023 mdyn A-’ for ZrCla2[23]. The same is also true among K(HfCl) = 1.980 and 1.564 mdyn A-’ for the CH,CN and CDXN complexes, 2.373 mdyn A-’ for HfCI,[12] and l.O57mdynW-’ for HfCl;*[23]. The force constant difference between K(M-Cl’) and K(M-

Study of Z&l, and HfCl, complexes with acetonitrile and acetonitrile-d3

Table 5. Calculated fundamental

wavenumbers and potential energy distribution for ZrC&.2CH,CN and ZrC14.2CD3CN

ZrCl4.2CH3CN ir calcd.

=1

a2

bl

b2

ZrCl4.2CD3CN PED

(%I*

D

PED

calcd.

(%)*

2996

loos,

2296

88S,,lOS,

2931

99s2

2219

YYSl

2292

8753,115~

2099

96s~

1395

YDSS

1086

6255.3557

1350

9255

1001

94s4

1021

8956

858

5457.3055

944

84~

802

94s6

404

49s17,43se

401

5os17,42ss

357

84sg,10s11

357

8559

312

91s10

311

93s10

244

74s11,14510

238

75s11.11s10

220

49512.33s13,11sl3

220

4Ys12,33s13,1ls8

160

46s15,26514S10513.10s16

159

46sl5,26slr,1osl3,1os16

126

34s1~,26s16,23s15

126

35514r27516r23515

106

47517,4osfj

105

47517.4lSz3

2996

!OOSl~

2219

99s1e

1395

9os19

1001

94s19

1021

8Yszo

802

94s20

401

5oszt+r45sz1

398

51sw+,44sz.1

204

8OS22.11%3

204

80522.11523

143

86523

143

86523

107

47s2br4lszl

106

47b,.41s21

2996

100526

2219

YYs26

1395

Y"s27

1001

94527

1021

8%23

802

94528

402

50s,,,~~s,,

399

5os3,.43s,g

336

94s30

336

94s30

215

88S3,

215

84531

162

98~32 4YS,,,44S,,

162

98s,z

107

4YS,,,45S,,

108

717

2996

1oos35

2295

87s,,,los,,

2931

YYs36

2219

99s35

2290

87537,11541

2099

96S36

1395

9os3e

1086

62s,g,34s,, 94s3,

1358

92539

1001

1021

89s40

854

6os41.31sgg

940

85s4,

802

94s40

397

5ls4,,46s,,

394

51s,8,45s,,

373

86S43

372

87s43

216

855,4,10543

210

84544

179

72s4,,14s,7

179

73s,5,14s,7

135

45s47,33s46,11s45

135

45s47,34s4,,11s,,

107

44s4,,38s4,,14s,,

106

44s,,,3Ys,,,13s,,

*Potential energy distribution. Terms below 10% are omitted.

Y. HASEand 0. L.

718

Table

6. Calculated

fundamental

wavenumbers

ALVES

and potential

energy distribution for HfC1,.2CH$N

and HfCl,.2CD3CN HfCl4.2CD3CN

HfCl4.2CH3CN 3

=1

a2

bl

b2

PED

calcd.

(%I*

iJ calcd.

PED

(%)*

2997

loos1

2297

aas3,10s7

2931

99s2

2219

YYS,

2292

875311157

2099

9652

1398

90%

1085

6255,3657

1357

9256

1003

9454

1021

89s6

862

54

948

a4s7

802

94j6

407

49S17.4356

405

5OS17,42S6

353

9659

353

96s9

310

9'510

309

93SlO

243

76s11,12slo

236

69s11

223

43s12,3as13.13s11

222

36s12,3Os13,2Os11

155

46515,25514

154

46515.25514

131

37S11+,27516,2ls16

131

38514,28516,21515

106

4as,,,41s,

105

48S17.4256

7,3055

2997

lOOS1a

2219

99S16

1398

9OS19

1003

94519

1021

89S20

802

94szo

405

5osz1+,45sz1

402

s~sz~,43%1

215

8lszz,lOs23

214

81s

149

87sz3

149

87s23

107

48szk,42s21

106

48szk,43sz1

2Z.:Os23

2997

loos26

2219

99s26

1398

9os27

1003

94%~

1021

89%

802

406

%,,,44s,g

403

5os33,43sz9

331

97s30

331

97s30

222

86S31

222

86S31

160

9as32

160

98s32

108

49s33r44S29

lo7

49s33,45sz9 8753?,lOS41

94s~

2997

100536

2295

2931

99S36

2219

99535

2290

87s37111541

2098

96s~

1398

90538

1084

62539.35541

1357

92s 39

1003

94S38

1021

90540

859

6Os41r3ls39

944

8ss41

802

94540

401

5ls~,46s42

397

5ls48,4%2

362

94s43

361

94s43

220

87sh4

212

87s44

178

76% s

178

77545

139

52sti7,38Sb6

138

52s47,38s46

108

46s~r41s~r1ls,+6

107

46546,42~42,11~4~

*See footnote to Table 5.

Study of Z&l,

and HfCl, complexes with acetonitrile and acetonitrile-dl

Cl”) is attributable to trans-influence by CH&N/CD$N and Cl. The ratios K(MCl’)/K(M-Cl”) are found to be almost constant and the values are 1.14, 1.16, 1.21 and 1.27 for the SnCl.+ TiCl,, ZrCL and HfCl, complexes, respectively. The ligand force constants obtained for the ZrCl, and HfCl, complexes are not essentially different by comparison with those for the TiCL and SnCI, complexes 171. Acknowledgements-The authors would like to thank Prof. K. KAWAI of the Toyama University for donating ZrC& and HfCl,. Y. H. wishes to acknowledge the Conselho National de Desenvolvimento Cientifico e Tecnol6gico (CNPq) for his research fellowship. REFERENCES [l]

[2] [3] [4] [5]

E. L. PACE and L. J. NOE, J. Chem. Phys. 49, 5317 (1968). M. P. MARZ~CCHI and M. G. MIGLIORINI, Spectrochim. Acta 29A, 1643 (1973). B. SWANSON and D. F. SHRIVER, Znorg. Chem. 9, 1406 (1970). D. F. SHRIVER and B. SWANSON, Znorg. Chem. 10, 1354 (1971). D. M. BYLER and D. F. SHRIVER, Znorg. Chem. 12,

1412 (1973). [6] D. M. BYLER and D. F. SHRIVER, Znorg. Chem. 13, 2697 (1974). [7] Y. KAWANO, Y. HASE and 0. SALA, J. Mol. Struct. 30,45 (1976).

719

HASE, C. AIROLDI, Y. GUSHIKEM and Y. KAWANO, Spectrosc. Lett. 9, 105 (1976). [9] Y. HASE, C. AIROLDI, Y. GUSHIKEM and Y. KAWANO, Spectrosc. Lett. 9, 177 (1976). 1101 Y. HASE, 0. L. ALVES and I. V. P. YOSHIDA, An.

[8] Y.

Acad. brasil. C&c. 51,93 (1979). 1111 _ _ W. M. GRAVEN and R. V. PETERSON,J. Znora. Nucl.

Chem. 31, 1743 (1969). [12] R. J. H. CLARK, B. K. HUNTER and D. M. RIPPON, Znorg. Chem. 11.56 (1972). [13] R. J. H. CLARK and D. M. RIPPON, J. Mol. Spectrosc. 44,479 (1972). 1141 D. M. ADAMS and D. C. NEWTON, J. Chem. Sot.(A) 2262 (1968). [15] T. L. BROWN,W. G. MCDUGLE, JR. and L. G. KENT, J. Am. Chem. Sot. 92,3645 (1970). [16] E. B. WILSON, JR., J. C. DECIUS and P. C. CROSS, Molecular Vibrations. McGraw-Hill, New York (1955). [I71 M. WEBSTERand H. E. BLAYDEN, J. Chem. Sot.(A) 2443 (1%9). [18] T. MIYAZAWA, Nippon Kagaku Zusshi 76, 1132 (1955). [19] D. E. MANN, T. SHIMANOUCHI,J. H. MEAL and L. FANO, J. Chem. Phys. 27,43 (1957). [20] Y. HASE, Computer Programs for Normal Coordinate Culculations (NCA-08). Universidade Estadual de Campinas, Campinas (1980). 1211 V. GUTMANN. Coordination Chemistrv in NonAqueous Solutions. Springer, New Yorki1968). [22] I. NAKAGAWA(ed.), Molecular Structure and Spectroscopy. Kyoritsu, Tokyo (1975). [23] W. BRONSWYK, R. J. H. CLARK and L. MARESCA, Znorg. Chem. 8, 1395 (1%9).