Inorganic chemistry of the transition elements vol 3 a review of chemical literature

Binary Compounds and Related Systems Halides and Oxyhalides Oxides Chalcogenides Carbides, Silicides, and Germanides Titaniumrr1 Halides and Oxyhalides 0-Donor Ligands S-Donor Ligands N-

A Specia I ist Period ica I Report

Inorganic Chemistry of

the Transition Elements

Volume 3

A Review of the Literature Published

between October 1972 and September 1973

Senior Reporter

Cambridge University

Rep0 rters

R Davis Kingston Polytechnic

C D Garner, Manchester University

L A P Kane-Maguire, University of Wales, Cardiff

J A McCleverty, University of Sheffkld

The Chemical Society

Burlington House, London, W I V OBN

ISBN: 0 851 86 520 8

Library of Congress Catalog Card No 72-83458

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

Preface

This, the third volume of the series, covers the period October 1972 to September

1973 and follows the layout adopted in the two previous volumes Chapter 1

Scandium, Yttrium, and the Lanthanides The Chemistry of the Elements of the first transition series from Manganese to Copper is discussed in Chapter 2

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

Binary Compounds and Related Systems

Halides and Oxyhalides Oxides

Chalcogenides Carbides, Silicides, and Germanides

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

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

Compounds with Elements of Group V and with Silicon 29

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)

Organometallic Vanadium(rI1) Compounds

Halides and Oxyhalides

0-Donor Ligands

Complexes with Ligands containing Oxygen and

S-Donor and Se-donor Ligands

61

61

64

Silicon, and with Germanium

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

Carbides and Silicides

Borides and Gallides

Halide and Oxyhalide Complexes

0-Donor Ligands

Polymeric Complexes containing Bridging Oxygen

Complexes with S-donor, Se-donor, or Te-donor

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

N-Donor Ligands Organometallic Compounds

7 Technetium and Rhenium

Technetium@) and Rhenium(@

Technetium@) and Rhenium(1v)

Technetium(v) and Rhenium(v)

Manganese@)

Halides and Pseudohalides Complexes

N-Donor ligands 0-Donor ligands S-Donor ligands Mixed donor ligands

Higher Oxidation States of Manganese 199

2 Iron

Carbonyl Compounds

Nitrogenyl and Nitrosyl Compounds

Other Iron(0) and Iron(1) Compounds

Iron(r1)

Halides and Pseudohalides

Hy drides 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

Halides and Pseudohalides Complexes

Iron(111)

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

Mixed donor ligands Other Cobalt@) Compounds Halides and Pseudohalides Complexes

Cobalt(Ir1)

Ammine and monoamine complexes Diamine complexes

Polyamine complexes Macrocyclic N-donor ligands and vitamin B Oximato-complexes

Other N-donor ligands 0-Donor, S-donor, Se-donor, and As-donor Amino-acid complexes

Schiff-base ligands Other mixed donor ligands Polynuclear anion-bridged complexes

Carbonyl, Nitrosyl, Nitrogenyl, and Oxygenyl

Halides and Pseudohalides

Other Compounds Nickel(rI1)

5 Copper

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

Oxides and Hydroxides Copper(II1)

0-Donor and S-donor ligands Molecular nitrogen complexes Nitrosyl complexes

Other N-donor ligands Sb-Donor ligands Si-Donor and Sn-donor ligands

Group VII Donors

Halide donor ligands Halogenophosphine complexes

Group VI Donors

0-Donor ligands S-Donor ligands N-Donor ligands C-Donor ligands

Group VII Donors

Other Donor Ligands

Group V Donors Group IV Donors

Group VII Donors

Hydrido-carbonyl and -phosphine complexes Halogeno-carbonyl and -phosphine complexes

Group VI Donors

0-Donor ligands S-Donor ligands N-Donor ligands

Group V Donors

Group IV Donors Group VI Donors

0-Donor ligands Group V Donors Group VII Donors Rhodium(rI1)

Halogeno-complexes Halogeno-carbonyl and -phosphine complexes Group VI Donors

0-Donor ligands S-Donor ligands N-Donor ligands P- and As-donor ligands

Halogeno-carbonyl and -phosphine complexes 0-Donor and S-donor ligands

N-Donor ligands P-Donor ligands Group VII Donors Iridium(II1)

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)

Mixed 0-donor and N-donor ligands Group VI Donors

Contents

S-Donor ligands Se-Donor ligands N-Donor ligands P-Donor and As-donor ligands C-Donor ligands

Sn-Donor and Pb-donor ligands

Mixed 0-donor and N-donor ligands S-Donor ligands

Se-Donor ligands N-Donor ligands P-Donor and As-donor ligands C-Donor ligands

Si-Donor, Sn-donor, and Pb-donor ligands

Group I11 Donors

B-Donor ligands

Group VII Donors Group VI Donors Group V Donors Group IV Donors

P-Donor, As-donor, and Sb-donor ligands Group IV Donors

A new type of fluxional process for an organometallic system has been des- cribed4 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(cyc1open- tadieny1)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

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

treatment of the corresponding aldehyde, a-keto-ester, acid chloride, or an- hydride with a mixture of [(n-Cp),TiCl,] and Mg-Mgl, (or EtMgBr) in a

This complex affords hydrazine when decomposed by HC1.'

A model olefin polymerization catalyst previously characterized as

titanium 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'

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

character The results of these calculations suggest that the R,Al group in the

C R Lucas, M Green, R A Forder, and K Prout, J.C.S Chem Comm., 1973.97

J.C.S Chem Comm., 1973, 169

l o 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

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

been shown to afford a convenient route to high-purity TiF,.', The thermo- dynamic relationships between the chlorides of titanium have been investigated and standard heats and entropies of formation of TiC13(l), Ti2C16(l), and

TiCl, or TiBr, by the reaction of titanium metal with molten metal halides

of TiCl,(g) has been recorded and discussed in comparison with available photoelectron data and theoretical results.' The energy required to reorganize

the self-consistent M O method The results suggest that the tetrahedral geo-

and the crystallization temperatures of the mixed halides TiCl,Br, TiCl,Br,,

TiCl,, TiBr,, [TiF6]'-, and binary mixtures of TiCl, with both TiBr, and TiI, have been determined The order of increasing shielding of the titanium

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

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

l 2 K Koyama and Y Hashimoto, Nippon Kagaku Kaishi, 1973,195 (Chem A h , 1973,78,91916~)

l 3 L D Polyachenok, G I Novikov, and 0 G Polpchenok, Obshchei priklad Khim., 1972, 34, 45

l4 H Elias and F Al-Khafagi, 2 anorg Chem., 1972,393,207

A A Iverson and B A Russell, Spectrochim Actu, 1973,29A, 715

l 6 B Hessett and P G Perkins, Rev Roumaine Chim., 1972,17, 611

l 7 G P Luchinskii, Zhur.fiz Khim., 1972,46,2959

l 8 (a) R G Kidd, R W Matthews, and H G Spinney, J Amer Chem SOC., 1972 94,6686; (b) V P

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-1 oxides has been classified as an infinitely adaptive one in crystallo- graphic 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 shown22 to be a sensitive indicator of their stoicheiometry, for 2 d n d 10, The structural aspects of the metal-insulator transition in T i 4 0 7 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

r e p ~ r t e d ~ '

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

metal atoms being C , , and r e ~ p e c t i v e l y ~ ~ The compounds Ni,TiS,

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 KnTiS2.29 Layer

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

B G Hyde and B N Figgis, Gout Report Announce ( U S A ) , 1972,72, 177

2 1 J S Anderson, J.C.S Dalton, 1973, 1107

2 2 J F Houlihan and L N Mulay, Materials Res Bull., 1971 6, 737

2 3 M Marezio, P D Dernier, D B McWhan, and J P Remeika, Materials Res Bull., 1970, 5,

2 4 L Brattas and A Kjekshus, Acta Chem Scand., 1972,26, 3441

2 5 C Perrin, A Perrin, and J Prigent, Efrll SOC chim France, 1972, 3086

2 6 L E Conroy and K R Pisharody, N a t Efrr Stand (U.S.A.) Spec Publ N o 364,1972,663

2 7 A Royer, A Le Blanc-Soreau, and J Rouxel, Compt rend., 1973,276, C , 1021

2 8 M Danot, J Bichon, and J Rouxel, Efill SOC Chim France, 1972,3063

3 1 A A Kuliev, Z G Kagramanyan, and D M Suleimanov, Ref Zhur met 1972, Abs 6138

1015; J Solid State Chem., 1973, 6, 213

Carbides, Silicides, and Germanides The standard heat of formation and the

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)

dynamic 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 TiSi2.33 Phase equilibria in the Ti-Nb-Ge ternary system have been investi- gated.34

tions 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

presence of AlC1, in benzene containing the polymethylbenzene These com- pounds, together with the analogous pentamethylbenzene derivative, may also

be prepared by ligand exchange reactions from C6H6TiC1,,A12C16 This study3*

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

[(7c-Cp),TiC12]-Li(NaFHg, [(n-Cp),TiC1,-J-[(7cc-Cp)Fe(CO),],, and [(n-C&-

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

species believed to be TiNMg,Cl,(THF),, and it is proposed that the mechanism

determining reaction with metallic Mg.40 The reactions of transition-metal

3 2 D L Cocke and K A Gingerich, J Chem Phys., 1972,57, 3654

3 3 G G Papin, 1 V Ryabchikov, N M Dekhanov, V G Mizin, and G V Serov, 2hur.jiz Khim.,

34 W Heller, 2 Mettalk., 1973,64, 124

3 5 J D Ellis, M Green, A G Sykes, G V Buxton, and R M Sellers, J.C.S Dalton, 1973, 1724

3 7 W E Smith, J.C.S Chem Comm., 1972, 1121

1972,46, 1558

complexes with azo-compounds are also of interest in connection with dinitro- gen 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 with HBr or NMe, to form TiBr,,B,Br,(NMe,H), or TiBr3,2NMe,, res- pectively ; pyrolysis affords B,Br,(NMe,),.47

42 C Floriani and G Fachinetti, J C S Ckern Comm., 1972, 790

4 3 A Merijanian, T Mayer, J F Helling, and F Klemick, J Org Chem., 1972 37.3945; A Meri-

4 5 E N Ryabov, I V Vasil'kova, L P Starikova, R A Sandler, and I V Godun, Zhur neorg

47 (a) M R Suliman and E P Schram Inorg Chem., 1973, 12, 923 (b) M R Suliman, Diss Abs

Khim., 1927, 17, 1759

17, 3111

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

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

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."

0.22 moll- '), and the presence of two electrochemically distinct titanium (111) complexes was observed Polarographic and e.s.r data were interpreted in

D,O ( 0 4 1 moll- ').'Ib However, conductance and electronic spectral data

TiC1, in MeOH under Ar, concentrating, and cooling to -80°C Solutions of TiCl, in Me,CHOH appear to contain [Ti(Me2CHOH)4C12]+ ions." Photo- reduction 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

been prepared by the reaction of the appropriate alcohol with [(1t-Cp)TiX,1

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 ~ ~

AcCl until all the solid was dissolved, followed by addition of Et,NCl Co- ordination of neutral acetic acid molecules is consistent with analytical and

acetic acid-acetic anhydride for 1-2 h affords an easy route to titanium(Ir1)

4 8 G P Shveikin and G V Bazuev, Zhur nrorg Khirn., 1973, 18, 291

4 9 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

678; (b) I B Goldberg and W F Goepplinger, Inorg Chem., 1972 1 1 3129

chem., 1972,76,1025, (Chem Abs 1972,37,158285~)

5 1 (a) E P Parry, 1 B Goldberg, D H Hern, and W F Goepplinger, J Phys Chem., 1973, 77,

5 2 B Pittel and W H E Schwars 2 anorg Chem., 1973, 3%, 152; Ber BunsengeseZlschajt Phys

5 4 R S P Coutts, R L Martin, and P C Wailes, Inorg Nuclear Chem Letters, 1973,9, 981

acetate 5 6 The reduction of titanium(1v) carboxylates and their DMF adducts

by hydrogen has been shown to afford Ti" species which act as catalysts for the hydrogenation of unsaturated organic molecules

In aqueous solution at 25"C, the heat of the reaction

Ti"' + 2H,C204 + Ti(C,04), + 4H'

at infinite dilution of Ti"', has been estimated5* as - 6 kJ rnol-' TiC1, reacts with OP(OBu'), at elevated temperatures to afford" [TiC12(OP(OBui),)], the electronic spectrum of which is consistent with hexaco-ordinated Ti"' The

crystal structure of [Ti(urea),](C10,), at 90 K is almost identical with that at room temperature with T i 4 bonds of length 200(2) rather than 204(1) pm.60 The magnetic anisotropy of [Ti(urea),]X, (X = I or ClO,) has been measured

between 80 and 300K and interpreted with the aid of a trigonally distorted octahedral ligand-field model.61 TiIn and alizarin form a 1: 1 complex (A,,, = 430nm) in aqueous solution.62 The sulphoxides R,SO (R = Bu, Ph, Bz, or p-C1C,H4) and Me(Ph)SO are reduced to the corresponding sulphides in

68-91 % yield by refluxing with TiC1, in MeOH-CHCl, under nitrogen.63

S-Donor Ligands The X-ray diffraction characteristics of La,TiBe2S14 have

been reported.64

N-Donor Ligands The electronic spectra, magnetic susceptibility, and e.s.r

spectra of [Ti(N(SiMe,),} 3] have been determined and interpteted using a crystal-field model for D,, symmetry.65 The crystal structure of trichlorotris- (pyridine)titanium(m)- 1 -pyridine has been shown to involve irregular co- ordination about the metal (7, the bond length variations appear to be a

n = 239.9 pin

\ / p y b = 235.1 pm T1 h c = 221.4 pm

V V Abalyaeva, 0 N Efimov, and M L Khidekel, Zzvest Akad Nauk S.S.S.R., Ser khim.,

1972, 1490, 1496

K Pan, S Hsin, and T Huang, J Chinese Chem SOC (Formosa), 1972, 19, 1, (Chem Abs., 1972,

77, 66924a)

C M Mikulski, L L Pytlewski, and N M Karayannis, J fnorg Nuclear Chern., 1973,352102

B N Figgis and L G B Wadley, Austral J Chem., 1972,25, 2233

B N Figgis, L G B Wadley, and M Gerloch, J.C.S Dalton, 1973, 238

G Colin and J Flahaut Bull Soc chim France, 1972,2207

E C Alyea, D C Bradley, R G Copperthwaite, and K D Sales, J.C.S Dalton, 1973, 185;

D C Bradley, R G Copperthwaite, S A Cotton, K D Sales, and J F Gibson, J.C.S Dalton,

consequence of steric rather than electronic effects.66 E.s.r and electronic spectra of [TiCl,(MeCN),] have been shown to be more consistent with a

mer- than fac-octahedral arrangement of the ligands [TiCl,(MeCN),] -t has

been prepared by the addition of a chloride acceptor (e.g AlCl, or TiCI,) to a

solution of anhydrous TiC1, in MeCN and the e.s.r and electronic spectra of this ion have been reported.67 14N-contact shifts have been measured for the complexes formed in MeCN solutions of TiCl,, and the observed negative coupling constants taken as evidence that spin-density is transferred from the

metal to the ligands via n-orbital overlap.68 The triplet-state X-band e.s.r

spectrum of dinuclear Ti"'-chelates of tetrakis(srminomethy1)methane has been recorded for frozen aqueous-glycol solutions (77 K) The spiro-conformation

of the methylene groups of this ligand ensures that the two metal centres in each dinuclear unit will have a non-parallel alignment of their g-tensor axes Interpretation of the spectrum has afforded a value of 560(30) pm for the Ti"'- Ti" separation in these d i m e r ~ ~ ~ E.s.r spectra have also been recorded for solutions of TiCl, in a wide range of organic bases (e.g MeCN, Et,N, py, or DMSO) and the data discussed in terms of monomer-dimer complex equi- libria.7

The i.r spectra of [Ti(bipy),]"+ complexes, in which the formal oxidation state of the metal ranges from 111 to -I, have been described in some detail11 Since the Ti-N stretching frequencies remain fairly constant over this range

of oxidation states, it is suggested that on reduction an increasing fraction of the electron population resides on the ligands, with the electron density at the metal remaining approximately constant This view is supported by the fact that the ligand spectra (1625-1475 and 1000-900 cm-') of the lower oxida- tion state complexes are similar to that of Li+(bipy)-

Mixed N-donor and 0-Donor Ligands Tris(quinolin-8-olato)titanium(111) has been prepared7, by the reaction of a-TiC1, and quinolin-8-01 in MeCN and characterized by magnetic susceptibility and e.s.r., electronic, and X-ray diffraction spectral studies Since the compound is isomorphous with the corres- ponding Al"' and Cr" derivatives it would appear to consist of mer-octahedral monomeric units, rather than dimeric units as previously suggested TiC1, reacts with diethyl 6-methylpyridine-2-phosphonate at elevated temperatures

to form tris(ethoxy-6-methylpyridine-2-phosphonato)titanium (111) Spectral data suggest that the ligand acts as a bidentate NO-chelate to give monomeric complexes which have a distorted octahedral geometry.73

6 h R K Collins and M G B Drew, Inorg Nuclear Chem Letters, 1972,8,975

6 7 H K Ostendorf, Rec Trau chim., 1972,91,809 (Chem Abs., 1972,77, 54457n)

6 a V K Kapur and B B Wayland, J Phys C h e m , 1973,77,634

6 9 S G Carr, P D W Boyd, and T D Smith, J.C.S Dalton, 1972, 1491

'O J B Raynor and A W L Ball, Inorg Chim Acta, 1973,7,315

(a) Y Saito, J Takemoto, B Hutchinson, and K Nakamoto, Inorg Chem., 1972, 11, 2003;

(6) E Koenig and E Lindner, Spectrochim Acta, 1972,28A, 1393

'' F B Taylor and T A Wilkins, J.C.S Dalton, 1973, 87

7 3 A N Speca, R Mink, N M Karayannis, L L Pytlewski, and C Owens, J Inorg Nuclear Chem.,

P-Donor Ligands TiC1,,2PEt3 and TiC1,,2PHflMe,-,, (n = 0-2) have been prepared by the direct combination of the components in toluene at elevated

air-sensitive and soluble in benzene, and TiC1,,2PEt3 has been shown to be monomeric in this medium E m and electronic spectral studies have shown

- 20 "C, but on warming one phosphine becomes detached.74 [TiCl,,PMe,-

PMe,,TiCl,] has been isolated and extensively characterized following the reaction between TiCl, and Me,PPMe, in MeCN, THF, or benzene.75

Na0,CR under anaerobic conditions in T H F followed by evaporation to dryness and sublimation of the residue at 180 "C affords these compounds as a

route from [(n-Cp)TiCl,] and RCO,H, in the presence of two moles of amine,

and Bu derivatives have shown that the compounds are dimeric The dia- magnetic nature of all of the compounds is considered to arise from a super-

electronic spectral properties have been recorded and interpreted on the basis

of discrete, hexaco-ordinate titanium(Ir1) centres Attempts to prepare the

diketones afforded the corresponding tris( P-diketonat0)titanium (111) complex [(n-Cp),TiF] has been prepared by reduction of [(n-Cp),TiF,] in THF with

by ligand exchange reactions with boron halides in the presence of A1 foil,

Me,C6H,, or 2,4,6-Me,C,H2) are monomeric with one unpaired electron per Ti"' These very air-sensitive complexes, prepared from [(n-Cp),TiCl] and RMgX under argon, react with dinitrogen to afford the deep-blue diamagnetic

7 5 K Issleib, U Giesder, and H Hartung, 2 anorg Chem., 1972,390, 239

R S P Coutts, R L Martin, and P C Wailes Austral J Chem., 1973,26, 47; 941

R S P Coutts, P C Wailes, and R L Martin, J Organometallic Chem., 1973,47, 375

7 7

7 8 J H Teuben and H J de Liefde Meijer, J Organometallic Chem., 1972, 46, 313; J H Teuben,

of these complexes contain no absorption characteristic of v(N-N) stretching

it is concluded that they have a centrosymmetric structure The complexed

Ph), which are initially green in THF, afford such blue solutions under N, or

amines have been obtained by treatment of the corresponding aldehydes, a-keto-esters, acid chlorides and anhydrides, or organolithium compounds with a mixture of [(n-Cp),TiCl,] and Mg-Mgl, (or EtMgBr) and a current of

oxidized by air and affords N2H4 on addition of HCl [{(n-Cp),Ti),N,MgCl]

(n-Cp),Ti-N-N=Ti(x-Cp), c* (n-Cp),Ti+-N=N - Ti(n-Cp),

I

MgCl

I

(8) MgCl

resonance hybrids, has been suggested.8 A new intermediate complex, [(n-

[(n-Cp),TiCl,]-MeMgI-N, The complex is stable at room temperature but loses N, above 40"C, it is apparently a di-imide derivative and initially affords

( p = 1.45 BM) and exhibits a v(N=N) stretching absorption at 1280 cm-I ;

different from the isomeric species described last year (Vol 2, p 2) The reactivity

which forms in the Volpin-Shur system has been characterized as [((x-Cp)Ti- C,H,] ,,6MgC1,,2Et20] This intermediate appears to be the reactive com-

7 9 T Chivers and E D Ibrahim, Canad J Chern., 1973,51, 815

Yu G Borodko, 1 N lvleva, L M Kachapina, S I Salienko, A K Shilova, and A E Shilov,

ponent of the mixture and reacts with N, in ethereal media to give a titanocene nitride derivative which affords NH, on hydrolysis.8

The crystal structure of [(n-Cp),Ti(BH,)] has been determined by X-ray diffraction studies and shown to involve molecular units in which the BH,

175(8) pm], thus producing quasi-tetrahedral co-ordination of the

The vibrational spectrum of [(n-Cp),Ti(BH,)] is consistent with the bidentate

catalyst, previously characterized as [(C,H,),TiHAlEt,] ,, has been shown by

characterized dimeric titanium-aluminiumalkyl hydride and structure (3) has been suggested.'

actions in octahedral titanium@) complexes has been discussed, and such interactions were shown to be important in determining the detailed structure

of such complexes and the preferential formation of certain isomers.84

Halides and Oxyhalides The 47Ti, 49Ti, and ''F n.m.r signals observed for

TiF, dissolved in 48% aqueous H F solutions have been shown'*" to be due

ion in such media The crystal structure of Li2TiF,,2H,O has been shown by

fluoride ions and water molecules containing the metal ions in distorted

mixture of TiO, and Ag,O (or Ag2S0,)87 and (HgI),[TiF,] by the ađition

fluoride perovskite KTi0,F has been prepared by the direct reaction of K F with TiO, under high pressure and its chemical and physical properties have been investigated." Mixtures of Na,TiF, and SiO, afford either Na,TiOF, or

X-ray diffraction studies have indicated that these products

substancệ'^

8 1 R H Marvich, Diss Abs (9, 1972,32, 6280

8 2 K M Melmed, D Coucouvanis, and S J Lippard, Inorg Chem 1973,12, 232

8 3 T J Marks, W J Kennelly, J R Kobb, and L Ạ Shimp, Inorg Chem., 1972,l

8 4 R F Zahrobsky, J Coord Chem., 1972,1, 301

8 5 Ẹ Ạ Marseglia and I D Brown, Acta Cryst., 1973, B29, 1352

8 6 N Ạ Parpiev, Uzbek khim Zhur., 1972, 16, 17(Chem Abs., 1973.78, 102621fl

8 7 B Miiller and R Hoppe, 2 anorg Chem., 1972,392, 37

D Breitinger and K Kohler, Inorg Nuclear Chem Letters, 1972,8 957

are specific

, 2540

D.t.a studies have shown9,= that, in the TiCl,-PCl, system, a 1 : 1 complex

symmetry for the anion.92b The standard enthalpy of formation of TiCl,

-690 kJ mo1-l at 25°C;93a when TiO, is dissolved in a NaCl-KCl melt

vapour pressure curve for the TiOC1,-NOCl system has indicated the forma-

crystalline solid This dissociates into its components at temperatures above

26 kJ mol-' The addition compounds NO[TiCl,(RCO,)] (R = Me, Et, Pr, Pr', or Bu') have also been reported in the TiCl,(RCO,)-NOCl systems but no evidence of NOCl addition to the corresponding TiCl,(RCO,), complexes

in the presence of hydrogenation catalysts such as PtO, or (Ph,P),RhCl at

MgCl, in alkali leads to the formation of detectable amounts of N2H4 This process can be made cyclic by subsequent acidification, and re-reduction of the TiIV by hydrogen.96

0-Donor Ligands Table 1 summarizes the results of some studies concerning titanates and TiIV mixed oxide compounds The corrosion of titanium metal

by liquid sodium containing dissolved oxygen has been shown to take place

Q 2 ( a ) M K Chikanova and E S Vorontsov, Zhur obshchei Khim., 1972, 42, 721; (b) D Nicholls and K R Seddon, Spectrochim Acta, 1972,28A, 2399

y 3 (a) V P Vasil'ev, P N Vorob'ev, and 1 B Khvostova, lzvest V U Z Khim i khim Tekhnol.,

1972, 15, 855 (Chem Abs., 1972,77, 80271s); (b) L M Gurevich and A B Bezukladnikov, Zhur neorg Khim., 1973, 18, 116

y 4 B Viard, J Amaudrut, and C Devin, Compt rend., 1973,276, C, 1279

y 5 J Amaudrut, Bull SOC chim France, 1972,2228

9h V V Abalyaeva, N T Denisov, M L Khidekel, and A E Shilov, lzoest Akad Nauk S.S.S.R.,

Ser khim., 1973, 196

97 M R Suliman and E P Schram, lnorg Chem., 1973,12,920

'* R J H Clark and M A Coles J.C.S Dalton, 1972,2454

Table 1 Some studies on titnnates and Ti" mixed oxides

I

BaC1,-TiC1,-NH,OH-H,O heptahydrate at 700 "C KOH-TiO,-SiO, NaF-Ti0,-SO,-H,O

TiO, + Sb,O, at > 900°C Ti0,-Bi,O,-KF-H,O TiIv + Bill1 hydroxide coppts

heated > 500°C

TiO, + TeO,

BaCO, + TiO, + 4-M203 NiO + TiO, at 2 1500°C

Table 1 (contd.)

Compound Source Properties reported

FeTiTaO, Fe,03 + TiO,-Ta,OS

at 1150-1250 "C under pressure fTio.04Moo.,,)0,.,o Ti02-Mo0,-Mo0, X , t.d.,

Izvest Akad Nauk S.S.S.R., neorg Materialy, 1972, 8, 1782 (e) 0 Matsumoto, K Ishida, and Y

Mitsuya, Denki Kagaku, 1972,40, 641 (Chem Abs 1972,77, 169805s) (fj K K Wu and I D Brown,

Acta Cryst., 1973, B29, 2009 ( g ) A 1 Savos'kina, T F Limar, and N G Kisel, Zhur neorg Khim.,

1972, 17, 2578 ( / I ) N G Shurnyatskaya V A Blinov, A A Voronkov, V V llvukhin, and N V Belov, Doklady Akad Nauk S.S.S.R., 1973, 208, 591 (i) V A Blinov, 0 K Mel'nikov, V V Ilyukhin,

A A Voronkov, and N V Belov, lzvest Akad Nauk S.S.S.R neorg Materialy, 1973, 9, 530

(k) B M Wanklyn, J Materials Sci., 1972, 7, 813 (0 A I Sheinkman, L M Gol'dshtein, V N Turlakov, and G V Kleshchev, Zhur priklad Khim., 1972, 45, 940 (m) M L Barsukova, V A

Kuznetsov, A N Lobachev, and T N Tanakina, Kristallografiya, 1972,17,846 (n) C G Macarovici

and G Morar, Z anorg Chem., 1972, 393, 275 (0) B I Danil'tsev, T T Mityureva, and I A Sheka,

Ukrain khim Zhur., 1972, 38, 526 (Chem Abs., 1972, 77, 169788~) (p) J Galy, Nat Bur Stand (U.S.A.), Spec Publ No 364, 1972, 29 (4) I E Grey and W G Mumme, J Solid State Chem., 1972,

5, 168 (r) R Masse Bull SOC franc Minkral Crist., 1972, 95, 405 (s) G Bayer and 0 W Florke,

Naturwiss., 1973,60, 102 (t) A 1 Sheinkman V G Mukhin, L M Gol'dshtein, and G V Kleshchev,

Ref: Zhur khim., 1972, Abs 6B842 (Chem Ahs., 1973, 78, 48847~) (u) A A Slobodyanyuk Yu D

Tret'yakov, and A F Bessonov, fzuest W Z , Tsvet Met., 1972, IS, 18 (Chem Abs., 1972,77, 131 549y)

(u) E I Krylov, F A Rozhdestvenskii, and V A Zavol'skii, U.S.S.R P 340622 (Cl.C.0lg) (Chem Abs., 1973, 78, 60442) ( w ) T Ekstrom, Acta Chem Scand., 1972, 26, 1843 (x) P V Klevtsov and

E A Zolotova, lzoest Akad Nauk S.S.S.R neorg Materialy, 1973, 9, 79 (y) H Miiller-Buschbaum and K Scheunemann, J Inorg Nuclear Chem., 1973, 35, 1091 (z) A K Borisov, E I Krylov, and

F A Rozhdestvenskii, Ref: Zhur khim., 1971, Abs 21B643 (Chem Abs., 1972,77, 96319~) (aa) L N Aver'yanova, V M Ezhov, and D V Balashov, Zhur neorg Khim., 1972, 17, 2842

by the formation of non-adherent ternary oxides, in addition to the well- known binary oxides and oxygen solid solutions in the metals Na,TiO, has been identified on the surface of titanium after immersion in liquid sodium containing dissolved oxygen at temperatures close to 600 "C The compound has been prepared by other routes and its composition confirmed by t.g.a.; its X-ray powder diffraction pattern indicates that it is a member of the iso-

structural Na,MO, (M = Ti, Sn, or Pb) The preparation and properties of potassium titanates have been re~iewed."~ The crystal structure

of Li,TiO, has been redetermined and shown to be a derivative of the NaCl- type with = 195 pm In Bi,Ti,O,, the T i 0 6 octahedra resemble those found in orthorhombic BaTiO,, with the T i 4 bond lengths ranging from

173 to 241 pm.' O0 A new cation-exchanger, titanium-zirconium phosphate, has been reportedlo' and the new thermally stable and highly strontium- specific ion-exchanger, titanium(1v) vanadate, has been prepared' O 2 by mixing

0.5M aqueous solutions of TiCI, and Na,VO, (pH 0-1) The new hetero-

polytungstates M4[Ti'VW802s] (M = Na, NH,, or T1) have been synthesized

from aqueous media (pH 5 5 4 5 ) ' 0 3

The oxidation of Ti"' to Ti" by OH radicals has been observed35 on pulse radiolysis of Ti"' solutions at pH 1.4 Stability constants have been reported for Ti(O€Q3+, Ti(OH)Z+, and Ti(OH); as 9.3 x l O I 3 1 mol-l, 1.5 x lo2' l2 mol-2, and 2.5 x lo3' l3 mol-,, r e s p e ~ t i v e l y , ' ~ ~ and the extent of polymer formation in the hydrolysis products of Ti'" has been studied by thin-layer gel-chromatography.' O 5

The crystal structures of two mononuclear peroxotitanium(1v) chelates, the red diaquoperoxotitanium(1v) dipicolinate, and the orange difluoroperoxo- titanium(1v) dipicolinate, have been determined Analogous to earlier results (Vol 1, p 3) the titanium atoms are co-ordinated approximately pentagonal bipyramidally, with the peroxo- and dipicolinato-chelates occupying the equatorial sites and the aquo- or fluoro-ligands the apical ones.lo6

The crystal structure of Nenadkevichite from Saint-Hilaire, Quebec, described : l o 7 other minerals in this series contain progressivelv more TiIV for NbV The mass spectrum of Ti(NO,), has been reported and, although no parent ion peak was observed, those corresponding to Ti(N0,); and TiO(NO,)+ were identified."' However, no substantial evidence could be provided for the ready loss of NO, radicals which has been postulated to explain the reactions of Ti(NO,), with organic molecules, The stepwise formation constants of TiOP,O; - at 20 "C in aqueous solution have been

Na3 76K0.2 4Ca0 1 1 Mn0.03(Nb2 7 6Til 1 8)02.f30(oH) 1 .20Si8024,H20 has been

'' (a) M G Barker and D J Wood, J.C.S Dalton 1972, 2448, 2451; (b) C Gicquel, M Mayer, and

R Bouaziz, Compr rend., 1972, 275, C , 1427

l o o A J Easteal and D J Udy, High Temp Sci., 1972, 4 487

l o ' J F Dorrian, Diss Abs ( B ) , 1972,32, 6587

lo' (a) S A Marei and S K Shakshooki Radiochem Radioanalyt Letters, 1972, 11, 187 (Chem

Abs., 1973 78, 172043~); (6) M Qureshi, K G Varshney, and S K Kabiruddin Canad J

Chem., 1972,50,2071

l o 3 G Marcu, R Vatulescu, and T Budiu, Stud Unia Babes-Bolyai, Ser Chem., 1972, 17, 87 (Chem Abs., 1973, 78, 790792)

C Liegeois, J Chim Phys Physicochem., Biol., 1972,69, 1531 (Chem A h , 1973, 78 10864j)

lo' M Sinibaldi, J Chromatogr., 1973,76,280

l o 6 D Schwarzenbach, Hell) Chim Acta, 1972 55, 2990

lo' G Perrault, C Boucher, J Vicat, E Cannillo and G Rossi, Acta Cryst., 1973 B29, 1432

35,

determined as 10'' 1 mol-' and 8.5 x lo3 1' mol-', respecti~ely.'~~ A new

and cubic phase of KTi,(POJ, has been prepared which is isotypic with

rhombohedra1 form of KTi,(PO,), has been shown to lead to the isotypic

and rn = 1.4-1.3), whose X-ray diffraction characteristics have been ob-

0.33, 1, 2, or 4) and their hydrates have been studied by spectroscopic and thermal analytical methods and it has been concluded from the results that

reacts'16 with LiCl in aqueous solution to form LiTiO(OH)SO, with a

H,SO, with an overall formation constant of 1.6 x lo3 1' mol-'

I o 9 L Sucha, Sbornik Vyscke Skoly Chem.-Technol Praze Analit Chem., 1972, 97 (Chem Abs., 1972,

77, 52895e)

R Masse, A Durif, J C Guitel, and 1 Tordjman, &ll Soc.fr.anG Minkral Crist., 1972, 95, 47

R C Paul, J K Puri, V P Kapila, and K C Malhotra J Inorg Nuclear Chem., 1972,34, 2141

'12 L 1 Bekkerman and 1 N Zadrodin, Zhur neorg Khim., 1972,17,2387

'13 R Perret and P Couchot, Compt rend., 1973,276, C , 507

745 (Chem Abs., 1973,78, 2 3 4 4 3 ~ ; 1972,77, 169812s); A M Sych and V V Garbuz, ibid., 1972,

38 1206 (Chem Abs., l973,78,51863b)

169420n)

11' I M Ryazantseva and N N Sel'manshuk, Izvest K U Z Khim i khim Technol., 1972,15, 947 (Chem Abs., 1972,77, 131 403w)

POC1, reacts with TiOCl, or [TiCl,(O,CR)] (R = Me, Et, Pr, Pr', or But) to

(11) with HOCH,P(O)PH (or its anilinium salt) or (HOCH,),P(O)OH affords

(12) or (13), respectively The action of (HOCH2),P(O)(OH),2PhNH, upon

in benzene solution and their i.r spectra determined.',," The dialkyl phosphite

been isolated following the reactions of TiCl, with the dialkyl phosphites in differing molar ratios in benzene solution under reduced pressure Their insolubility and i.r spectra suggest that these compounds are polymeric with

> l o 5 1 mol-', 8 1, rnol-,, and lo-' l3 mol-,, re~pective1y.l~~

dissociate in DMF solution to form the ions [TiCl(RCO,),]+ and [TiCl, (RCO,)]-, and the uptake of hydrogen by these solutions in the presence of

acid) have been prepared by mixing solutions of Bi(NO,), and H,[TiO(C,O,),],

for the hydrated and anhydrous forms, the latter being obtained by heating

1 1 Ti'v-2,4-dihydroxybenzoic acid complex'25 of stability constant 3 x

2.1 x lo8, 1.4 x lo", and 1.7 x 10l8 1 mol-l, respectively, have been charac- terized

of partially carboxylated products.127 Formylation of methyl 2,4-dihydroxy-

lZo T D Ibraeva, Yu A Nevskaya, and T A Sumarokova, Ref: Zhur khim 1972, Abs 5B1479

(Chem Abs., 1973,78, 10989d)

l Z 2 (a) A A Muratova, E G Yarkova V P Plekhov, R G Zagetova, and A N Pudovik, Zhur obshchei Khim., 1972,42,976; (b) D M Pun and A Parkash, J Indian Chem SOC., 1972,49,833

l Z 3 V V Yastrebov, Zhur.fiz Khim., 1972,46,2922

lZ4 C Gh Macarovici and Gh Morar, Reti Roumaine Chim., 1972, 17, 847; Stud Unio Babes-

l Z 5 A I Astakhov, E N Knyazeva, and S Ya Schnaiderman, Zhur obshchei Khim., 1972,42,2505

Bolyai, Ser C h e w 1972,17, 5 (Chem Abs., 1973,78,66432j)

benzoate and related compounds with C1,CHOMe and TiC1, affords the

OMe

The standard heat of formation of Ti(OEt), (s) has been determined',' calori-

MeCOCH2C02(CH2),0,CCH2COMe (H,L; n = 2,4, or 5) in 2 : l and 1 :1

molar ratios with substitution of one and two alkoxide groups, respectively,

The reaction of TiCl, with NH, followed by treatment with 2 : l R'OH-H20

pectively.'34 The chloro(alkoxy)bis-(2,4-pentanedionato)titanium(1v) com-

alkoxypentachlorotitanium(rv) salts (pyH),[(RO)TiCl,J have been reported

by the addition of hexane, produces [Cl(RO)Ti(acac),] The 'H n.m.r spectra

of these latter complexes contain only one peak at room temperature, but at lower temperatures in CHC1, solution the patterns observed are consistent

1972 27, 2272; D Kh Petkova, S Ya Schnaiderman, and E N Knyazeva, Zhur obshchei

13' U B Saxena, A K Rai, and R C Mehrotra, Z Naturforsch, 1972, B27, 1145

l J 3 A D Pomogailo, D V Sokol'skii, U A Mambetov, E M Gluzman, and G G Kochurovskaya

Doklady Akad Nauk S.S.S.R., 1972,207, 882

with the cis-octahedral isomer being the dominant solution species.'35 A similar geometry has been identified by X-ray diffraction studies for three bis- chelate complexes of bis-(2,6-di-isopropylphenoxo)titanium( rv) with two 2,4- pentanedionato-, 8-quinolato-, or 2-methyl-8-quinolato-groups as the other

ligands All three compounds are monomeric with distorted octahedral co- ordination about the titanium(Iv1 and all have approximately two-fold molecular symmetry The lengths of the T i 4 bonds involving the phenoxy- ligands range from 183.4 pm in the acetylacetonate to 181.6 pm in the quin- aldate ' 36 Di-p -oxo-bis-(2,4-pentanedionato)titanium( IV), and its bis-dioxan adduct, have been characterized by X-ray crystallographic studies and shown

to be cyclic dimers, the two metal centres being linked by two oxygen atoms The di-p-0x0-dititanium ring is planar with L OTiO and L TiOTi 83 and 97", respectively.137

Some fourteen crystalline 1 : 1 and 1 :2 TiC1,-cycloalkanone complexes have been prepared and their carbonyl stretching frequencies shown to be 40-77 cm-' lower than those exhibited by the uncomplexed groups; the integrated intensities of the carbonyl stretching modes were shown to be a measure of the relative basicities of the ketones towards TiC1, The enthalpies of addition

of these complexes were seen to be dependent on the number of carbon atoms

in the cycloalkanone ring and steric effects of methyl substituents ct to the

carbonyl 1 : 1 and 2: 1 TiIV-purpurin and 1 :2 TiIv-naphthazarin complexes have been characterized spectrophotometrically.'3g 1 : 1 and 1 :2

(BuO),TiCl,-, ( n = 0-4) and THF, dioxan, and tetrahydr~pyran'~' have been characterized Low-temperature "F n.m.r spectra of solutions containing TiCl,, TiF,, and 1,2-dimethoxyethane (DME) have shown that halogen redistribution occurs to produce all possible mixed-halide complexes con- taining a single cis-chelated DME ligand These results, together with those of the analogous THF system suggest that, in the absence of steric interactions,

the preferred orientation involves fluoride trans to the 0-donor ligand, pre-

sumably because of the enhanced n-bonding ability of the fluorine in this orientation 142a Related systems involving TiI, gave very poor spectra apparently because of rapid ligand exchange effects.142b

S-Donor Ligands The 'H and I3C n.m.r spectra of [Ti(S,CNPr,),] have been obtained as part of a general study of ligand inequivalence in eight-co-ordinate

77, 6681 9~) Yu A Lysenko, V N Marchenko, L I Khokhlova, and A I Pletnev, Zzvest, V.U.Z Khim i khim Technol., 1973,16, 177 (Chem Abs., 1973,78, 152 150x)

c0mp1exes.l~~ Seven-co-ordinate tris(dialkyldithiocarbamato)titanium(Iv) hal-

anhydrous NaS2CNR2 to a solution of TiX, in CH2C12 These complexes appear to exist as monomeric molecular units, from molecular weight and mass spectral data, and their i.r spectra are consistent with the presence of

complexes in CH2C12 at room temperature indicate that they are non-rigid

to afford [C1,TiS2PF,], whose ''F n.m.r spectrum contains only the sharp doublet expected from this formulation The complex is air- and solvent- sensitive and its low volatility has been ascribed to a chloride-bridged poly-

thiol, respectively, have been isolated and characterized In each case T i 4

N-Donor Ligands (Me,Si),N reacts with TiCl, to yield the novel heterocyclic

reacts with N-metalled cyclic amines to afford the corresponding [(R,N),Ti-

4HC1, react with diethylketone to form TiO,, the corresponding amine, and

been prepared from their constituent molecules by mixing in a chlorinated

characterized, where L is a unidentate, aromatic Schiff base derived from

benzaldehyde, anisaldehyde, or salicylaldehyde and amines such as aniline,

spectra of these complexes are consistent with octahedral stereochemistry

143 E L Muetterties, Inorg Chem., 1973, 12, 1963

146 J A Douek and J T Spickett, J lnorg Nuclear Chem., 1973, 35, 511

399

strukt Khim., 1973, 14, 70

G E Manoussakis and J A Tossidis, J lnorg Nuclear Chem., 1972,34,2449

about the Ti" involving N-bonded ligands L.' 5 2

prepared by mixing THF solutions of TiC1,,6H20 and the appropriate aromatic nitrogen base.' 53

Mixed N-donor and 0-donor Ligands The five-co-ordinate bis(a1koxy)-

[(R20),Ti(NMeCH,CH,NMeJ] (R2 = Et or P?) have been prepared by the

addition of the lithium salt of the appropriate bidentate ligand to [(RO),TiCl]

in a suitable solvent under a nitrogen atmosphere These compounds are all

consistent with covalent, monomeric units containing chelated ligands The analogous [(EtO),Ti(OCHRCH,NMe,)] complexes are dimeric and are pre- sumed to involve tris-octahedral Ti" centres linked by bridging ethoxy-

treating Ti(OR), compounds with ligands such as 7-allyl-8-hydroxyquino-

temperature to form {Ti(ox),},O

Titanyl perchlorate dissolved in the minimum quantity of aqueous alcohol

(HL), under analogous conditions, react to give monomeric [TiOL,] com- plexes and i.r spectral studies suggest that these complexes are five co-ordinate,

structure has been proposed'57 for the 1 :1 complexes formed by T i 0 2 + and the Schiff bases (17) These compounds have been obtained from methanolic

solution as dark, microcrystalline solids which are soluble in DMF and

Schiff bases (18) (20); the i.r spectra of (18) show that the nitrogen of the

being trans-octahedral.'

Ann Unio Bucaresti, Chem., 1971,20, 39 (Chem Abs., 1973,78, 5 1 9 0 9 ~ )

1 5 3 M M Khan, lnorg Nuclear Chem., 1972,34,3589

154 E C Alyea and P H Merrell, lnorg Nuclear Chem Letters, 1973,9, 69

156 (a) N S Biradar, V B Mahale, and V H Kulkarni, J Znorg Nuclear Chem., 1973, 35, 2565;

157 N S Biradar, V B Mahale, and V H Kulkarni, Znorg N u c l e a Ckem Letters, 1972, 8, 997

Zhur obshchei Khim., 1972,42,566

l S 9 (a) R C Aggarwal, B N Yadav, and T Prasad, lndian J Chem., 1972,10,671; (6) R C Aggarwal, (6) N S Biradar and V B Mahale, J Less-Common Metals, 1973, 31, 159