Taking TiF4 complexes to extremes - the first examples with phosphine co-ligands

Jura, Marek, Levason, William, Petts, Edmund, Reid, Gillian, Webster, Michael and Zhang, Wenjian (2010) Taking TiF4 complexes to extremes - the first examples with phosphine co-ligands. Dalton Transactions, 39 (42), 10264-10271. (doi:10.1039/c0dt00747a). (PMID:20882256)

Abstract

The first soft donor adducts of TiF4, [TiF4(diphosphine)] (diphosphine = o-C6H4(PMe2)2, R2P(CH2)2PR2, R = Me or Et) have been prepared from [TiF4(MeCN)2] and the diphosphines in rigorously anhydrous CH2Cl2, as extremely moisture sensitive yellow solids, and characterised by multinuclear NMR (1H, 31P, 19F), IR and UV/visspectroscopy. The crystal structure of [TiF4{Et2P(CH2)2PEt2}] has been determined and shows a distorted six-coordinate geometry with disparate Ti–FtransF and Ti–FtransP distances and long Ti–P bonds. Weaker soft donor ligands including Ph3P2P(CH2)2PPh2, o-C6H4(PPh2)2, Ph2As(CH2)2AsPh2, o-C6H4(AsMe2)2 and iPrS(CH2)2SiPr do not form stable complexes with TiF4, although surprisingly, fluorotitanate(IV) salts of the previously unknown doubly protonated ligand cations [LH2][Ti4F18] (L = o-C6H4(PPh2)2, o-C6H4(AsMe2)2 and iPrS(CH2)2SiPr) are formed in some cases as minor by-products. The structure of [o-C6H4(PPh2H)2][Ti4F18] shows the first authenticated example of a diprotonated o-phenylene-diphosphine. The synthesis and full spectroscopic characterisation are reported for a range of TiF4 adducts with hard N– or O-donor ligands for comparison purposes, along with crystal structures of [TiF4(thf)2], [TiF4(Ph3EO)2]·2CH2Cl2 (E = P or As), and [TiF4(bipy)].

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Contributors

Author: William Levason

Author: Gillian Reid

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