Tritertiary arsine complexes of titanium(IV) and zirconium(IV) halides

Barclay, G. A.; Gregor, IK; Lambert, MJ; Wild, S. B.

doi:10.1071/ch9671571

Cited by 6 publications

(3 citation statements)

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“…Cl( 1)-Ti(1)-Cl( 3) Cl( 2)-Ti(1)-Cl( 3) Cl(3)-Ti(1)-Cl( 4) Se( 1)-Ti(1)-Cl( 1) Se (1)-Ti(1)-Cl(3) Se(2)-Ti(1)-Cl(1) Se(2)-Ti(1)-Cl(3) Cl(1)-Ti(1)-Cl(2) 2.727(1) 2.239(2) 2.267 (2) 163.11 (7) 93.14 (6) 94.87( 6) 87.20( 5) 80.74( 5) 84.41 (5) 81.00(4) 94.94( 6)…”

Section: Reaction Of Ticlmentioning

confidence: 99%

“…2.308(2) 2.744(1) 2.231 (2) 96.42( 7) 109.28 (7) 74.42(3) 162.48 (6) 87.69( 5) 88.46(5) 162.05 (6) Table 5 Selected bond lengths (Å) and angles (Њ) for 1) Ti( 1)-S( 2) Ti( 1)-Cl( 2) Cl( 2)-Ti(1)-Cl( 3) Cl( 2)-Ti(1)-Cl( 5) Cl( 2)-Ti(1)-S( 1) Cl( 2)-Ti(1)-S( 2) Cl(3)-Ti(1)-Cl( 5) Cl(3)-Ti(1)-S( 2) Cl( 5)-Ti(1)-S( 1) Cl( 5)-Ti(1)-S(2) 2.653(2) 2.624(2) 2.300 (2) 160.80 (7) 96.79( 7) 77.82( 6) 87.94( 6) 94.12( 7) 78.80( 6) 90.92( 6) 169.18 (7) Ti( 1)-Cl( 3) Ti(1)-Cl( 5) Ti( 1 6) 165.39 (7) 86.40( 5) 95.27( 6) 86.28( 6) 97.66( 6) 180.00 102.77 (6) longer than those observed in the mononuclear species above. Related oxo-bridged dinuclear Ti species are known, e.g.…”

Section: Reaction Of Ticlmentioning

confidence: 99%

“…The bromo and iodo species were included since the volatility and decom-position behaviour of this class of compound is expected to vary with halogen. There are very few well characterised TiI 4 complexes in the literature, 6…”

Section: Introductionmentioning

confidence: 99%

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Hard/soft interactions in early transition metal chemistry: synthesis, properties and structures of thioether and selenoether complexes of titanium(IV)

Levason

Patel

Reid

et al. 2000

J. Chem. Soc., Dalton Trans.

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Reaction of TiCl 4 with L-L [L-L = MeE(CH 2 ) n EMe; E = S or Se, n = 2 or 3, PhE(CH 2 ) 2 EPh or o-C 6 H 4 (EMe) 2 ] in anhydrous n-hexane solution under an N 2 atmosphere results in the rapid formation of [TiCl 4 (L-L)] as yellow, orange or red solids. Analogous bromo and iodo species, [TiX 4 (L-L)] [X = Br; L-L = MeE(CH 2 ) n EMe or o-C 6 H 4 (EMe) 2 ; X = I; L-L = MeSe(CH 2 ) 2 SeMe or o-C 6 H 4 (SeMe) 2 ], were obtained as intense orange or red coloured solids by treatment of TiX 4 with L-L in CH 2 Cl 2 solution. Crystallographic studies on [TiCl 4reveal a distorted octahedral arrangement with the coordinated group 16 donor ligand adopting the  form in the first three cases and the meso form in the fourth example. These studies also reveal a trans influence series of Cl > S ≈ Se on Ti(). Solution NMR studies show that the chloro-compounds undergo rapid pyramidal inversion at ambient temperature, while the bromo and iodo species also undergo rapid ligand dissociation/chelate ring-opening. At low temperature these processes are slowed significantly, such that in most of the chloro and bromo species it is possible to identify both the meso and  invertomers, although ligand exchange is still rapid at 200 K for the iodo species. The potential of these compounds as sources of titanium sulfide or titanium selenide phases via controlled decomposition is also discussed briefly. Finally, the dinuclear species, [Cl 3 Ti{MeS(CH 2 ) 2 SMe}] 2 (µ-O), formed by partial hydrolysis of [TiCl 4 {MeS(CH 2 ) 2 SMe}], has also been identified crystallographically.

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