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A Specia Iist PeriodicaI Report

Inorganic Chemistry of
the Transition Elements
Volume 3

A Review of the Literature Published
between October 1972 and September 1973

Senior Reporter
6. F. G. Johnson, University Chemical Laboratory,
Cambridge University
Rep0rters

R. Davis. Kingston Polytechnic
C. D. Garner, Manchester University
L. A. P. Kane-Maguire, University of Wales, Cardiff
J. A. McCleverty, University of Sheffkld

@ Copyright 1974

The Chemical Society
Burlington House, London, W I V OBN

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ISBN: 0 85186 520 8
Library of Congress Catalog Card No. 72-83458

Printed in Gt. Britain by Page Bros (Norwich) Ltd, Norwich


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Preface
_

_

_

_

~

~

~

This, the third volume of the series,covers the period October 1972to September
1973 and follows the layout adopted in the two previous volumes. Chapter 1
contains an account of the Chemistry of the Early Transition Metals, excluding
Scandium, Yttrium, and the Lanthanides. The Chemistry of the Elements of
the first transition series from Manganese to Copper is discussed in Chapter 2.

Chapter 3 deals with the Noble Metals (Ru, Os, Rh, Ir, Pd, Pt, Ag, and Au)
and Chapter 4 with the Lanthanides (includingSc, Y, and La) and the Actinides.
We thank readers for their advice and constructive criticisms of Volumes 1
and 2, and we have attempted to put some of the suggested modifications into
practice. We hope to receive further constructive criticisms of this volume.
B. F. G. JOHNSON


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Contents

Chapter 1 The Early Transition Metals
By C. D. Garner

1

1 Titanium
Introduction
Binary Compounds and Related Systems
Halides and Oxyhalides
Oxides
Chalcogenides
Carbides, Silicides, and Germanides
Titanium (11)
Titanium(rr1)
Halides and Oxyhalides

0-Donor Ligands
S-Donor Ligands
N-Donor Ligands
Mixed N-Donor and 0-Donor Ligands
P-Donor Ligands
Cyclopentadienyl Complexes
Titanium (IV)
Halides and Oxyhalides
0-Donor Ligands
S-Donor Ligands
N-Donor Ligands
Mixed N-donor and 0-donor Ligands
Organometallic Titanium(1v) Compounds
Titanium-Carbon o-Bonded Complexes
Cyclopentadienyl Complexes

5
6
6
7
8
8
9
10
10
12
12
13
20
21

22
23
23
26

2 Zirconium and Hafnium
Introduction
Binary Compounds and Related Species
Halides and Oxyhalides
Oxides and Chalcogenides
Compounds with Elements of Group V and with Silicon

27
27
28
28
28
29

V

1
1

3
3
4

4
5



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Contents

vi

Zirconium(I1) and Hafnium(1r)
Zirconium(n1) and Hafnium(rI1)
Zirconium(rv) and Hafnium(1v)
Halides and Oxyhalides
0-Donor Ligands
S-Donor Ligands
N-Donor Ligands
Mixed N-donor and 0-donor Ligands
Organometallic Zirconium(1v)and Hafnium(1v)
Compounds
o-Bonded Complexes
n-Bonded Complexes
Zirconium(1v) and Hafnium(1v) Hydrido-compounds
3 Vanadium
Introduction
Carbonyl and other Lowoxidation State Compounds
Nitrosyl Complexes
Binary Compounds and Related Species
Halides
Oxides
Chalcogenides
Compounds with Elements of Group V
Hydrides

Vanadium(r1)
Vanadium(rr1)
Halides and Oxyhalides
0-Donor Ligands
S-Donor Ligands
N-Donor Ligands
Mixed N-donor and 0-donor Ligands
Cy ano-complexes
Organometallic Vanadium(rI1) Compounds
Vanadium(1v)
Halides and Oxyhalides
0-Donor Ligands
Complexes with Ligands containing Oxygen and
other Donor Atoms
S-Donor and Se-donor Ligands
N-Donor Ligands
Sb-Donor Ligands
Organometallic Compounds
Mixed-valence Compounds
Vanadium(v)
Halides and Oxyhalides
0-Donor Ligands

29

29
30
30
30
36

37
37
38
38

39
39
40
40
41
42
42
42
42
43
43
44
44
45
45
45
47
47
47
48
48
48
48
49
53

56
58
58
58

61)
61

61
64


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Contents

vii

N-Donor and Mixed N-donor and 0-donor Ligands
Organometallic Compounds

67
68

4 Niobium and Tantalum
Introduction
Carbonyl Complexes
Binary Compounds and Related Systems
Halides
Oxides
Chalcogenides

Compounds with Elements of Group V, with
Silicon, and with Germanium
Hydrides
Compounds with Nb-Nb or Ta-Ta Bonds
Niobium(II1) and Tantalum(rr1)
Niobium(rv) and Tantalum(1v)
Niobium(v) and Tantalum(v)
Halides and Oxyhalides
0-Donor Ligands
S-Donor and Se-donor Ligands
N-Donor and Mixed N-donor and 0-donor Ligands
Organometallic Complexes

68
68
70
70
70
70
72

5 Chromium
Introduction
Carbonyl Complexes
Organometallic n-Complexes
Trifluorophosphino-complexes
Dinitrogen Complexes
Nitrosyl Complexes
Binary Compounds and Related Systems
Halides

Oxides
Chalcogenides
Compounds with Elements of Group V
Carbides and Silicides
Borides and Gallides
Hydrides
Chromium(I1)
Halides
0-Donor Ligands
N-Donor Ligands
Organometallic Compounds
Chromium(II1)
Optically Active Complexes

72
73
73
74
74
76
76
78
85
85
86
87
87
88
92
94

94
94
95
95
96
96
97
97
97
98
98
98
98
99
100
100
100


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. ..

Contents

Vlll

Halide and Oxyhalide Complexes
0-Donor Ligands
Polymeric Complexes containing Bridging Oxygen
Atoms

Complexes with S-donor, Se-donor, or Te-donor
Ligands
N-Donor Ligands
Mixed N-donor and Other Donor Atom Ligands
P-Donor Ligands
Cyano-complexes
Organometallic Compounds
Chromium(1v)
Chromium(v)
Chromium(v1)
Halides and Oxyhalides
0-Donor Ligands
N-Donor Ligands

6 Molybdenum and Tungsten

Introduction
Carbonyl Complexes
Trifluorophosphino-complexes
Dinitrogen Complexes and Nitrogen Fixation
Nitrosyl Complexes
Cyano- and Isocyano-complexes
Hydrido-complexes
Binary Compounds and Related Systems
Halides
Oxides
Chalcogenides
Other Binary and Related Systems
Compounds containing Mo-Mo or W-W Bonds
Molybdenum(r1) and Tungsten@)

Molybdenum(II1) and Tungsten(II1)
Molybdenum(1v) and Tungsten(1v)
Molybdenum(v) and Tungsten(v)
Mononuclear Complexes
Dinuclear and Polynuclear Complexes
Molybdenum and Tungsten Bronzes
Molybdenum(v1) and Tungsten(v1)
Halide, Oxyhalide, and Related Complexes
0-Donor Ligands
Iso- and Hetero-polyanions
S-and Se-Donor Ligands

101
102
105
108
109
111
113
113
115
116
116
116
117
117
118
120
120
120

122
128
128
131
133
134
135

135
137
137
138
138
142
142
144
146
146
148
150
151
151
154
162
165


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Contents

N-Donor Ligands
Organometallic Compounds

166
166

7 Technetium and Rhenium
Introduction
Carbonyl Complexes
Dinitrogen Complexes
Nitrosyl Complexes
Cyanide Complexes
Hydrido-complexes
Binary Systems and Related Compounds
Halides
Oxides
Nitrides and Borides
Compounds with Tc-Tc or Re-Re Bonds
Technetium@) and Rhenium(@
Technetium@) and Rhenium(1v)
Technetium(v) and Rhenium(v)
Rhenium(v1)
Technetium (VII)and Rhenium(vI1)

167
167
168
171

172
172
173
173
173
174
174
175
176
176
178
179
179

8 Appendix

181

Chapter 2 Elements of the First Transitional Period
By R. Davis

185

1 Manganese
Carbonyl Compounds
Nitrosyl Compounds
Other Manganese(1) Complexes
Manganese(@
Halides and Pseudohalides
Complexes

N-Donor ligands
0-Donor ligands
S-Donor ligands
Mixed donor ligands
Oxides
Manganese@)
Halides and Pseudohalides
Complexes
N-Donor ligands
0-Donor ligands
S-Donor ligands
Mixed donor ligands

185
185
190
191
191
191
191
191
193
195
195
197
197
197
197
197
198

198
198


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Contents

X

Higher Oxidation States of Manganese
2 Iron

Carbonyl Compounds
Nitrogenyl and Nitrosyl Compounds
Other Iron(0) and Iron(1) Compounds
Iron(r1)
Halides and Pseudohalides
Hydrides
Complexes
Pyridine and related ligands
Macrocyclic N-donor ligands
Other N-donor ligands
0-Donor ligands
S-Donor and P- donor ligands
Mixed donor ligands
Iron(111)
Halides and Pseudohalides
Complexes
N-Donor ligands
0-Donor ligands

S-Donor and Se-donor ligands
Mixed donor ligands
Iron(rv) Compounds
Higher Oxidation States of Iron
Oxides, Hydroxides, and Sulphides

3 Cobalt
Carbonyl Compounds
Nitrogenyl and Nitrosyl Compounds
Cobalt(1)
Cobalt(I1)
Halides and Pseudohalides
Hydrides
Complexes
Amine complexes
Pyridine and related ligands
Imidazole, pyrazole, and related ligands
Macrocyclic N-donor ligands
Other N-donor ligands
0-Donor ligands
S-Donor and Se-donor ligands
P-Donor and As-donor ligands

199
200
200
210
21 1
21 1
21 1

212
213
213
214
217
218
220
221
222
222
223
223
224
226
226
227
227
227

228
228
232
234
235
235
236
236
236
237
238

239
240
241
245
245


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Contents

Mixed donor ligands
Other Cobalt@) Compounds
Cobalt(Ir1)
Halides and Pseudohalides
Complexes
Ammine and monoamine complexes
Diamine complexes
Polyamine complexes
Macrocyclic N-donor ligands and vitamin B
analogues
Oximato-complexes
Other N-donor ligands
0-Donor, S-donor, Se-donor, and As-donor
ligands
Amino-acid complexes
Schiff-base ligands
Other mixed donor ligands
Polynuclear anion-bridged complexes

Cobalt@) and Cobalt(v)
Oxides
Cobalt- Oxygen Compounds

4 Nickel

Carbonyl, Nitrosyl, Nitrogenyl, and Oxygenyl
Compounds
Halides and Pseudohalides
Nickel(0)
Nickel(1)
Nickel(1.5)
Nickel(I1) Complexes
Ammine, Amine, and Related Ligands
Pyridine and Related Ligands
Imidazole and Pyrazole Ligands
Macrocyclic N-donor Ligands
Other N-donor Ligands
0-donor Ligands
S-Donor and Se-donor Ligands
P-Donor and As-donor Ligands
Mixed Donor Ligands
Other Compounds
Nickel(rI1)
Nickel(1v)
Oxides

247
252
252

252
253
253
254

256
258
260
26 1
262
263
265
266
268
268
268
268

270
270.
270
27 1
27 1
272
27 3
273

27 5
275
276


279
280
284
285
287
296
296
297
297


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xii

Contents

5 Copper
coPPer(1)
Halides
Complexes
N-Donor and 0-donor ligands
S-Donor and Se-donor ligands
P-Donor ligands
Mixed donor ligands
Other Copper(1) Compounds
Copper(I1)
Halides
Complexes
N-Donor ligands

0-Donor ligands
S-Donor and Se-donor ligands
Mixed donor ligands
Copper(II1)
Oxides and Hydroxides

298
298
298
298
298
299
300
301
30 1
30 1
301
303
303
309
313
314
325
325

6 Ligands

325

7 Formation and Stability Constants


328

8 Bibliography

333

Chapter 3 The Noble Metals
By L. A. P. Kane-Maguire
1 Ruthenium
Cluster Compounds
Ruthenium(0) and Ruthenium(1)
Rut henium(I1)
Group VII Donors
Halogeno-carbonyl and -phosphine complexes
Hydridophosphine complexes
Group VI Donors
0-Donor and S-donor ligands
Group V Donors
Molecular nitrogen complexes
Nitrosyl complexes
Other N-donor ligands
Sb-Donor ligands
Group IV Donors
Si-Donor and Sn-donor ligands
Mixed Oxidation State Ruthenium

337
337
337

339
340
340
340
341
342
342
343
343
344
345
347
347
347
348


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xi11

Contents

Ruthenium(rI1)
Group VII Donors
Halide donor ligands
Halogenophosphine complexes
Group VI Donors
0-Donor ligands

S-Donor ligands
Group V Donors
N-Donor ligands
Group IV Donors
C-Donor ligands
Ruthenium(1v)
Group VII Donors
Other Donor Ligands
Ruthenium(1v) and Ruthenium(vI1r)
2 Osmium

Cluster Compounds
Osmium(0)
Osmium(I1)
Group V Donors
Molecular nitrogen complexes
Other N-donor ligands
Other Group Donors
Osmium(rI1)
Osmium(1v)
Osmium(v)
Osmium(v1)

3 Rhodium
Cluster Compounds
Rhodium( -I)
Rhodium(1)
Group VII Donors
Hydrido-carbonyl and -phosphine complexes
Halogeno-carbonyl and -phosphine complexes

Group VI Donors
0-Donor ligands
S-Donor ligands
Group V Donors
N-Donor ligands
P- and As-donor ligands
Group IV Donors
Rhodium(I1)
Group VI Donors

349
349
349
349
349
349
349
352
352
353
353
353
353
354
354
354
354
356
356
356

356
358
359
3 59
360
361
36 1
36 1
36 1
362
363
363
363
364
365
365
366
367
367
369
370
370
370


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Contents

xiv
0-Donor ligands

Group V Donors
Rhodium(rI1)
Group VII Donors
Halogeno-complexes
Halogeno-carbonyl and -phosphine complexes
Group VI Donors
0-Donor ligands
S-Donor ligands
Group V Donors
N-Donor ligands
P- and As-donor ligands

370
371
371
372
372
372
372
372
373
374
374
378

4 Iridium
Cluster Compounds
Iridium( -I)
Iridium(1)
Group VII Donors

Halogeno-carbonyl and -phosphine complexes
Group VI Donors
0-Donor and S-donor ligands
Group V Donors
N-Donor ligands
P-Donor ligands
Iridium(II1)
Group VII Donors
Halogeno-complexes
Halogeno-carbonyl and -phosphine complexes
Group VI Donors
0-Donor ligands
S-Donor ligands
Group V Donors
Group IV Donors
C-Donor and Sn-donor ligands
Iridium(1v)

379
379
379
380
380
380
38 1
38 1
382
382
383
384

384
384
384
386
386
386
387
390
390
39 1

5 Palladium
Palladium(0)
Palladium(I1)
Group VII Donors
Halide and hydride donor ligands
Halogeno-phosphine and -phosphite complexes
Group VI Donors
0-Donor ligands
Mixed 0-donor and N-donor ligands

393
393
393
393
393
394
394
394
395



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Contents

S-Donor ligands
Se-Donor ligands
Group V Donors
N-Donor ligands
P-Donor and As-donor ligands
Group IV Donors
C-Donor ligands
Sn-Donor and Pb-donor ligands
Palladium(1v)
6 Platinum
Cluster Compounds
Platinum(0)
Platinum(11)
Group VII Donors
Halogeno-complexes
Halogenophosphinecomplexes
Group VI Donors
0-Donor ligands
Mixed 0-donor and N-donor ligands
S-Donor ligands
Se-Donor ligands
Group V Donors
N-Donor ligands

P-Donor and As-donor ligands
Group IV Donors
C-Donor ligands
Si-Donor, Sn-donor, and Pb-donor ligands
Group I11 Donors
B-Donor ligands
Platinum(1v)
Group VII Donors
Group VI Donors
Group V Donors
Group IV Donors
Platinum(v)

7 Silver
Silver(1)
Group VII Donors
Group VI Donors
0-Donor ligands
S-Donor ligands
Group V Donors
N-Donor lieands

396
400
400
400
402
403
403
404

404
406
406
406
409
409
409
409
41 1
41 1
412
413
417
417
417
420
42 1
421
421
422
422
422
422
423
423
423
424
426
426
426

430
430
43 1
432
432


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Contents

xvi

P-Donor, As-donor, and Sb-donor ligands
Group IV Donors
Silver-Metal Bonded Compounds
Silver@)
Silver(n1)

433
434
434
434
435

8 Gold
Cluster Compounds
Gold(r)
Group VII Donors
Group VI Donors
Group IV Donors

Gold(r1r)
Group VII Donors
Group VI Donors
Group V Donors
Gold(v)

436
436
439
439
439

9 Reviews

443

440
440
440
440
44 1
442

Chapter 4 Scandium, Yttrium, the Lanthanides, and the Actinides
By J. A. McCleverty
446
1 Scandium and Yttrium
Structural Studies
Chemical Studies


446
446
446

2 The Lanthanides
Structural Studies
Chemical Studies
Lanthanide Shift Reagents

448
449
45 1
460

3 TheActinides
Structural Studies
Chemical Studies

463
463
466

4 Uranyl and Related Compounds
Structural Studies
General Chemistry

472
472
475


Author Index

48 1


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1
The Early Transition Metals
BY C. D. GARNER
1 Titanium
Introduction.-A text describing the chemistry of titanium has been published'
and the organometallic chemistry of titanium reported during 1971 has been
reviewed.2 The compound C8H,TiC,Ph, has been prepared by treating
TiCl, with Pr'MgBr in ether containing cyclo-octatetraene and diphenylacetylene. This green compound is diamagnetic and air-stable in the solid
state and its i.r., mass, and 'H n.m.r. spectra are consistent with a structure
involving .n-bonded cyclo-octatetraene and tetraphenylcyclobutadiene rings.3
A new type of fluxional process for an organometallic system has been described4 for bis(cyc1o-octatetraene)titanium(u) in which formal oxidation and
reduction occur for the planar and bent C8H8 rings, (I), respectively, through
reciprocal ring bending and flattening with an activation energy of 70 f 1 k.T
mol-'.

Cyclopentadienyl(cycloheptatrieny1)titanium has been shown by an X-ray
diffraction study to be a sandwich compound, the dihedral angles between
the C,H5 and C7H7 rings being 2.2". Although the distance of the titanium
atom from the carbon atoms of the former ring (232 pm) is normal, that from
the carbon atoms of the latter (219 pm) is unusually short5 Tris(cyc1opentadieny1)titanium involves two h5- and one h2-C5H, groups (2); it is suggested
that in the bonding of this latter group to the metal, the cyclopentadienyl
radical acts as a three-electron ligand thus giving the titanium a 17-electron
G . P. Luchinskii, 'The Chemistry of Titanium', Khimiya, Moscow, 1971

F. Calderazzo, J. Organometallic Chem., 1973,53, 179.
H. 0.Van Oven, J . Organometallic Chem., 1973,55, 309.
J. Schwartz and J. E. Sadler, J.C.S. Chem. Comm., 1973, 172.
J. D. Zeinstra and J. L. de Boer, J . Organometallic Chem., 1973,54. 207.

1


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Inorganic Chemistry of the Transition Elements

2

configuration. This three-electron h2-C,H, arrangement may serve as a model
for the intermediate state in the 1,2-shift mechanism in fluxional 7t-C5H5
systems.6
The fixation of dinitrogen by organic compounds in the presence of titanocene
derivatives has been accomplished, and amines can be obtained directly by
treatment of the corresponding aldehyde, a-keto-ester, acid chloride, or anhydride with a mixture of [(n-Cp),TiCl,] and Mg-Mgl, (or EtMgBr) in a
current of d i n i t r ~ g e nThe
. ~ paramagnetic complex [{(7c-Cp),Ti),N2MgC1] has
been isolated at - 60 "C in the system [(n-Cp),TiCl,]- Pr'MgC1-N, in ether.
This complex affords hydrazine when decomposed by HC1.'
A model olefin polymerization catalyst previously characterized as
[(C,H,),TiA1Et,12 has been studied by X-ray diffraction, 'H n.m.r., and mass
spectral techniques. The compound contains ( l-%-C5H5) andp(1-5q :o-C,H,)
rings and is the first well-characterized dimeric titanium-aluminium hydride :
structure (3) has been suggested.' Alkyl exchange between a polymeric alkyltitanium compound and alkylaluminium compound, present in excess, is

usually assumed to be the main transfer process in Ziegler-Natta olefin

polymerization. Such an exchange process has been identified" between
TiMe, and A1,Me6. M O calculations have been performed along the reaction
coordinate for the insertion of ethylene into a titanium-carbon o-bond'
and also for the titanium-aluminium-ethylene complex (4).' I b These latter
results showed that the Ti-olefin bond involves no back-bonding and that the
.n*-orbital of the olefin acquires little stability on co-ordination to titanium.
The Ti-Me bond of (4)is localized almost completely in the highest bonding
level of the complex, with the metal contribution being almost pure d in
character. The results of these calculations suggest that the R,Al group in the

lo

C. R . Lucas, M. Green, R. A. Forder, and K. Prout, J.C.S. Chem. Comm., 1973.97.
A. Dormond, J. C. Leblanc. F. Le Moigne, and J. Tirouflet, Compt. rend., 1972,274, C . 1707.
Yu. G. Borodko, 1. N. Tvleva, L. M. Kachapina, E. F. Kvashina, A. K. Shilova, and A. E. Shilov,
J.C.S. Chem. Comm., 1973, 169.
F. N. Tebbe and L. J. Guggenberger, J.C.S. Chem. Comm., 1973,227.
A. S. Khachaturov, L. S. Bresler, and 1. Ya. Poddubnyi, J . Organometallic Chem., 1972,42, C18.
(a) P. Cossee, P. Ros, and J. H. Schachtschneider, Proceedings of the 4th International Congress
on Catalysis, 1968, 1, 207 (Chem. A h . 1972, 77, 88946m); (6) D. R. Armstrong, P. G. Perkins,
and J. J. P. Stewart, J.C.S. Dalton. 1972, 1972.


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The Early Transition Metals

3

molecular catalyst functions merely as a substrate which maintains a high
co-ordination number at the titanium site. Calculations along the reaction

co-ordinate indicate that the negatively charged methyl group may readily
migrate to the olefin, which carries a net positive charge, consistent with the
phenomenon of catalysis.
Binary Compounds and Related Systems.- -Halides and Oxyhalides. Thermal
decomposition of NH,TiF, in a H, or Ar atmosphere at 6 0 0 4 5 0 ° C has
been shown to afford a convenient route to high-purity TiF,.', The thermodynamic relationships between the chlorides of titanium have been investigated
and standard heats and entropies of formation of TiC13(l), Ti2C16(l), and
TiOCl(s) determined as - 525 kJ mol-' and 328 e.u., - 1180 kJ mol-' and
520 e.u., and - 760 kJ mol-' and 75 e.u., re~pectively.'~
The preparation of
TiCl, or TiBr, by the reaction of titanium metal with molten metal halides
such as PbX,, AgX (X = C1 or Br), or CuCl has been studied at 450-550 "C.
The reaction of titanium with an excess of molten PbCl, at 530°C affords
pure TiC1, in 9.8 % yield after 15 min.I4 The vacuum-u.v. electronic spectrum
of TiCl,(g) has been recorded and discussed in comparison with available
photoelectron data and theoretical results.' The energy required to reorganize
TiC1, from tetrahedral to various other geometries has been evaluated by
the self-consistent MO method. The results suggest that the tetrahedral geometry is a consequence of nuclear repulsions rather than bonding interactions.I6
An equilibrium diagram has been constructed for the TiC1,-TiBr, system
and the crystallization temperatures of the mixed halides TiCl,Br, TiCl,Br,,
and TiClBr, were shown to be - 19.4, -5.7, and 13.4 "C, respectively.
These liquids have standard heats of formation of - 760, - 710, and - 660 kJ
mol-', re~pective1y.l~
The chemical shift data for the 47Ti and ,'Ti n.m.r. of
TiCl,, TiBr,, [TiF6]'-, and binary mixtures of TiCl, with both TiBr, and
TiI, have been determined. The order of increasing shielding of the titanium
nucleus by the halogens is 1,Br < C1. The resonance absorptions for TiCl,
and TiBr, are unshifted on dilution in inert solvents, thus suggesting that the
neat liquids of these halides involwe monomeric molecules. Mixtures of TiCl,
and TiBr, exhibit one resonance signal, the chemical shift of which varies

linearly with the mole fraction of the components, consistent with rapid
halogen exchange between the TiCl,Br,_, (x = 0-4)molecules. A similar
exchange process probably takes place between two or more species in TiC1,Til, mixtures since again only one signal is observed.lSa Raman spectra of
TiCl, solutions in BrCH,OMe show lines typical of the TiCl,,Br,-,, (n = 1 - 4 )
molecules.' 8 b
l2
l3

l4
l6
l7
l8

K. Koyama and Y. Hashimoto, Nippon Kagaku Kaishi, 1973,195 (Chem. A h . , 1973,78,91916~).
L. D. Polyachenok, G. I. Novikov, and 0. G. Polpchenok, Obshchei priklad Khim., 1972, 34, 45.
H. Elias and F. Al-Khafagi, 2. anorg. Chem., 1972,393,207.
A. A. Iverson and B. A. Russell, Spectrochim. Actu, 1973,29A, 715.
B. Hessett and P. G. Perkins, Rev. Roumaine Chim., 1972,17, 611.
G. P. Luchinskii, Zhur.fiz. Khim., 1972,46,2959.
(a) R. G. Kidd, R.W. Matthews, and H. G. Spinney, J . Amer. Chem. SOC.,
1972 94,6686; (b) V. P.
Makridin and S. 1. Chistyakov, Z h u r ohslichei Khim.. 1972.42, 1871.


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Inorganic Chemistry of the Transition E Eements

4

Oxides. The structures and properties of titanium dioxide have been reviewed1'

and the bonding in anatase has been suggested to be more ionic than that in
rutile from a study of their K X-ray emission spectra.20 The structure of the
Tin02n-1oxides has been classified as an infinitely adaptive one in crystallographic shear phases (4 < n < 9 and 16 < n < 3 9 . 2 1 The linewidths of the
e.s.r. spectra of these oxides has been shown22to be a sensitive indicator of their
stoicheiometry, for 2 d n d 10, The structural aspects of the metal-insulator
transition in Ti407 have been investigated by X-ray crystallography. The
triclinic structure of this oxide consists of rutile-like layers of TiO, octahedra
extended in the ab-plane and four octahedra thick along the c-axis. At 120 K
there is a clear separation into strings of TiIn or Ti" ions running parallel to the
c-axis; the Ti'' centres are paired to form Ti-Ti bonds, whereas the Ti"
atoms are strongly bonded to one oxygen, T i 4 = 178-179
Chalcogenides. The composition of TiS, has been shown to be 1 :3.00 by X-ray
diffraction and density measurement~,~
and its vibrational spectra have been
rep~rted.~'
The mixed cation disulphides Ti0.05V1.00S2,
Tio.84Vo.16S2,
Tio~70Cro~ogS2,
and Ti0.92Cro,09S2
have been prepared by grinding a mixture of TiS, with
the appropriate metal and sulphur, followed by prolonged heating at 950 OC.,,
Ti,.,,,NbS, has been shown to have a structure in which the titanium atoms
occupy octahedral sites between the NbS, prisms, the site symmetries of the
re~pectively.~~
The compounds Ni,TiS,
metal atoms being C,, and
(x = 0.25, 0.33, 0.40, or 0.75) have been characterized in the Ni-TiS, system
by X-ray diffraction studies. These compounds probably involve nickel atoms
inserted into octahedral sites of the host lattice.28 TiS, reacts with solutions of
K'(naphtha1ene)- to give a metal intercalation derivative KnTiS2.29Layer

intercalation compounds of TiS, with NH,, N,H4, NH,NHMe,
MeNHNHMe, and py, other nitrogen heterocyclics, and their N-oxides have
been prepared, and the layer expansions determined.30
The phase diagrams of the Ti-Hg-Se and TiSe-HgSe systems have been
constructed using X-ray and thermal analyses and a compound of composition
Ti,Hg7Selo was identified in the latter.31

2o
21

22

23

24
25
26

27
28
29

30
31

B. G. Hyde and B. N. Figgis, Gout. Report Announce. (U.S.A.),1972,72, 177.
M . Pessa and E. Suoninen, Phys. Letters (A), 1972,40,407.
J. S. Anderson, J.C.S. Dalton, 1973, 1107.
J. F. Houlihan and L. N. Mulay, Materials Res. Bull., 1971. 6, 737.
M. Marezio, P. D. Dernier, D . B. McWhan, and J. P. Remeika, Materials Res. Bull., 1970, 5,

1015; J . Solid State Chem., 1973, 6, 213.
L. Brattas and A. Kjekshus, Acta Chem. Scand., 1972,26, 3441.
C. Perrin, A. Perrin, and J. Prigent, Efrll. SOC.chim. France, 1972, 3086.
L. E. Conroy and K. R. Pisharody, Nat. Efrr. Stand (U.S.A.)Spec. Publ. N o . 364,1972,663.
A. Royer, A. Le Blanc-Soreau, and J. Rouxel, Compt. rend., 1973,276, C , 1021.
M. Danot, J. Bichon, and J. Rouxel, Efill. SOC.
Chim. France, 1972,3063.
E. Bayer and W. Riidorff, Z . Naturforsch, 1972,27b, 1336.
R. Schollhorn and A. Weiss, Z . Naturforsch., 1972, 274 1273, 1275, 1277; 1972. 27% 1428.
A. A. Kuliev, Z. G. Kagramanyan, and D. M. Suleimanov, Ref Zhur. met.. 1972, Abs. 6138
(Chem. Abs.. 1973,78. 1026075).


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The Early Transition Metals

5

Carbides, Silicides, and Germanides. The standard heat of formation and the
dissociation energy of TiC,(g) have been determined as - 730 k 9 and
160 f 8 kJ mol-l, respectively, using the mass spectrometric Knudsen
effusion technique.32 The standard heat and entropy of formation of Ti,Si,(s)
have been reported as - 580 kJ mol-' and 272 e.u., re~pective1y.l~
A thermodynamic analysis of the co-reduction of TiO, with SiO, by carbon at elevated
temperatures has shown that the formation of TiSi is more probable than
TiSi2.33Phase equilibria in the Ti-Nb-Ge ternary system have been investigated.34
Titanium@).-Pulse radiolysis of aqueous solutions of titanium(rI1) containing
formic acid affords Ti" ziia reduction of Ti"' by -C02H.35Density determinations of molten NaCl solutions (800-950 "C) of TiCl, suggest that substantial
amounts of [TiCl,]- are formed in such media.36 The d-d spectrum of Ti"
ions isolated in NaCl crystals have been obtained, and absorption maxima

identified at ca. 8000 and 15000 cm-' and assigned to ,Tlg
-,3T2gand
Tlg -+ Tlgtransitions, respectively. The samples were prepared from CdC1,
and titanium metal in NaCl at 950 0C.37
Titanium@) complexes, ArTiC1,,A1,C16 (Ar = tetra-, penta-, or hexa-methylbenzene), may be prepared by the reduction of TiCl, with metallic A1 in the
presence of AlC1, in benzene containing the polymethylbenzene. These compounds, together with the analogous pentamethylbenzene derivative, may also
be prepared by ligand exchange reactions from C6H6TiC1,,A12C16.This study3*
has provided further support for the n-interaction between titanium and the
aromatic molecules suggested earlier.
New evidence has been presented indicating the participation of Ti" in
various dinitrogen-fixing systems, although other studies of these systems
(p. 10) indicate that Ti"' is also involved. An investigation of the systems
[(7c-Cp),TiC12]-Li(NaFHg, [(n-Cp),TiC1,-J-[(7cc-Cp)Fe(CO),],, and [(n-C&TiCl,]-Na[(n-Cp)Fe(CO),] has led to the conclusion that the active species
for dinitrogen absorption is probably titanocene, with perhaps more than one
molecule of dinitrogen bonded to each titanocene dimer.39 The kinetics and
stoicheiometry of dinitrogen fixation by TiC1,-Mg mixtures in T H F solution
have been reported. These systems react with N, at 25 "C (1 atm) to form a
species believed to be TiNMg,Cl,(THF),, and it is proposed that the mechanism
involves the complexing of N, with a dimeric Tin species, followed by a ratedetermining reaction with metallic Mg.40 The reactions of transition-metal
32
33

34

35
36

37
38
39

40

D. L. Cocke and K. A. Gingerich, J. Chem. Phys., 1972,57, 3654.
G. G. Papin, 1. V. Ryabchikov, N. M. Dekhanov, V. G. Mizin, and G. V. Serov, 2hur.jiz. Khim.,
1972,46, 1558.
W. Heller, 2. Mettalk., 1973,64, 124.
J. D. Ellis, M. Green, A. G. Sykes, G. V. Buxton, and R. M. Sellers, J.C.S. Dalton, 1973, 1724.
D. J. MacDonald, P. R. Bremner, and A. E. Raddatz, J . Chem. Eng. Data, 1973,18, 187.
W. E. Smith, J.C.S. Chem. Comm., 1972, 1121.
S. Pasynkiewicz,R. Giezynski, and S. Dzierzgowski,J . Organometallic Chem., 1973,54, 203.
C. Ungurenasu and E. Streba, J . Inorg. Nuclear Chem., 1972,34, 3753.
A. Yamamoto, S. Go, M. Ookawa, M. Takahishi, S. Ikeda, and T. Keii, Bill. Chem. SOC.Japan,
1972,45,3110.


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Inorganic Chemistry of the Transition Elements

6

complexes with azo-compounds are also of interest in connection with dinitrogen fixation. [(n-Cp),Ti(CO),] reacts during two days at 25 "C with azobenzene
to form black-maroon crystals of [(n-Cp),Ti(Ph-N=N-Ph)]
which are
thermally stable, soluble in aromatic hydrocarbons but readily hydrolysed :
structure (5)has been suggested.,'

(5)

Oxidative additions of alkyl and acyl halides to [(n-Cp),Ti(CO),] affording
Ti" derivatives have been reported42 (p. 25). Titanocene has been shown to

reduce a variety of organic molecules including alcohols, aldehydes, ketones,
and organic halides.43
Titanium(Irr).-HaZides and Oxyhalides. Semi-empirical MO calculations on
[TiF6I3- using a new parameter-free method have been published, and the
calculated and experimental values of the ligand-field splitting, super-hyperfine
coupling constants, and spin densities were in excellent agreement.44
Density determinations of NaCl solutions (800-950°C) containing TiC1,
have led to the suggestion that substantial quantities of [TiCl,]- are formed
under these condition^.,^ The phase diagram for the TiC1,-NaC1-AlCl,
system has been presented; Na,TiCl6 is the only compound formed.45 A
thermal analysis of the TiCl,-VCl,-KCl system has been performed and the
only compounds identified were K,MC16 (M = Ti or V).46
Treatment of TiBr, with B,(NMe,), produces TiBr,,B,Br,(NMe,),, which
has been characterized by i.r. and electronic spectral and magnetic studies as
a dinuclear species: structure (9 has been suggested. The compound reacts
or TiBr3,2NMe,, reswith HBr or NMe, to form TiBr,,B,Br,(NMe,H),
pectively ; pyrolysis affords B,Br,(NMe,),.47
Br
Me,NBHBr

/

I

Br

Br

\Ti'


I

\Br/
Br

'Ti

I /Br\BNMe,
/
I \Br- BNMe,

Br

(6 1
G. Fachinetti, G. Fochi, and C. Floriani, J . Organometakc Chem., 1973, 57, C51.
C. Floriani and G. Fachinetti, J.C.S. Ckern. Comm., 1972, 790.
43 A. Merijanian, T. Mayer, J. F. Helling, and F. Klemick, J . Org. Chem., 1972. 37.3945; A. Merijanian, T. Maver. and J. F. Helling, Reu. Latinoamer. Quim.. 1972.3.62(Chem. Abs. 1973,78,4324s).
44 A. Dutta-Ahmed and E. A. Boudreaux, Znorg. Chem., 1973, 12, 1597.
4 5 E. N. Ryabov, I. V. Vasil'kova, L. P. Starikova, R. A. Sandler, and I. V. Godun, Zhur. neorg.
Khim., 1927, 17, 1759.
46 R. A. Sandler, E. N. Ryabov, I. V. Vasil'kova, and E. A. Cherepanova, Zhur. neorg. Khim., 1972,
17, 3111.
47 (a) M. R. Suliman and E. P. Schram Inorg. Chem., 1973, 12, 923. (b) M. R. Suliman, Diss. Abs.
(B), 1972.33. 621.
41

42


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The Early 'TLansitionMetals

7

0-Donor Ligands. YTiO, has been prepared from Ti,O, and Y,O, and its
X-ray diffraction characteristics have been reported.48 TiTaO, has been
obtained from the corresponding oxides by ceramic techniques under an inert
atmosphere ; X-ray and neutron diffraction and magnetic measurements
indicate that the metal atoms are distributed statistically over the metal sites
of the rutile structure.49 Treatment of an aqueous HCl solution of titanium(@
chloride with alkali affords a dark-brown precipitate of Ti,O,,nH,O, which is
rapidly oxidized to TiO,,nH,O via a blue-black intermediate. The reflectance
spectrum of the latter is very similar to that of the corresponding iron system
and therefore the intermediate probably involves oxygen bridging between
Ti"' and Ti" centres."
The electrochemical behaviour of the Ti"-Ti'" couple has been investigated
in methanol solutions containing H,O (0.02-7.00 moll- ') and C1- (0.020.22 moll- '), and the presence of two electrochemically distinct titanium (111)
complexes was observed. Polarographic and e.s.r. data were interpreted in
terms of the species [TiCl,(MeOH),] +,[TiCl(MeOH)5]Z+,and [TiCl(MeOH),.
H,O]' +,the former two complexes equilibrating rapidly on an electrochemical
t i m e - s ~ a l e . Analogous
~~"
results were obtained for TiCl, in MeOD containing
D,O ( 0 4 . 1 moll- ').'Ib However, conductance and electronic spectral data
indicate that TiC1, in ROH (R = Me or Et) also produces [Ti(ROH),I3+, and
crystalline [Tj(MeOH),]Cl, has been prepared by refluxing a 5 % solution of
TiC1, in MeOH under Ar, concentrating, and cooling to -80°C. Solutions of
TiCl, in Me,CHOH appear to contain [Ti(Me2CHOH)4C12]+ ions." Photoreduction of a titanium(1v)alkoxide in aqueous solution containing an alcohol
or a glycol has been shown to generate Ti'= species and alkoxyl radicals ria
homolytic cleavage of a Ti"-OR

bond.53The polymeric alkoxides (RO)TiCl,,2ROH (R = Me or Et), (MeO)TiBrZ,2.7MeOH,and (EtO)TiBr,,2EtOH have
been prepared by the reaction of the appropriate alcohol with [(1t-Cp)TiX,1
(X = C1 or Br). These alkoxides are diamagnetic; their electronic spectra are
consistent with octahedral co-ordination about the metal, and their i.r. spectra
with bridging a l k o x y - g r ~ u p s . ~ ~
E ~ , N [ T ~ C ~ , ( A C O Hhas
) ~ ~been prepared by refluxing TiC1,,6H,O in
AcCl until all the solid was dissolved, followed by addition of Et,NCl. Coordination of neutral acetic acid molecules is consistent with analytical and
spectroscopic data.55 Refluxing titanium(1v) salts with Na-Hg in 1 : 1 glacial
acetic acid-acetic anhydride for 1-2 h affords an easy route to titanium(Ir1)
48

49

51

52

53
54
55

G. P. Shveikin and G. V. Bazuev, Zhur. nrorg. Khirn., 1973, 18, 291.
D. N. Astrov, N. A. Kryukova, R. B. Zorin, V. A. Makarov, R. P. Ozerov, F. A. Rozhdestvenskii,
V. P. Smironov, A. M. Turchaninov, and N. V. Fadeeva, KristallograJiya, 1972, 17, 1152.
G. C. Allen, M. B. Wood, and J. M. Dyke, J . Inorg. Nuclear Chem., 1973,35,2311.
(a) E. P. Parry, 1. B. Goldberg, D. H. Hern, and W. F. Goepplinger, J . Phys. Chem., 1973, 77,
678; (b) I. B. Goldberg and W. F. Goepplinger, Inorg. Chem., 1972. 1 1 . 3129.
B. Pittel and W. H. E. Schwars 2.anorg. Chem., 1973, 3%, 152; Ber. BunsengeseZlschajt Phys.
chem., 1972,76,1025, (Chem. Abs. 1972,37,158285~).

F. E. McFarlane and G. W. Tindall, Inorg. Nuclear Chem. Letters, 1973,9, 907.
R.S. P. Coutts, R. L. Martin, and P. C. Wailes, Inorg. Nuclear Chem. Letters, 1973,9, 981.
L. P. Podmore, P. W. Smith, and R. Stoessiger, J.C.S. Dalton, 1973, 209.