Dicarbonylbis(η-cyclopentadienyl)titanium(II) chemistry: reactions with organic molecules containing C–Cl, P–Cl, O–H, and S–Cl bonds; synthesis, properties, and structures of η-acyl derivatives of titanium(IV)
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 23,p. 2297-2302
- https://doi.org/10.1039/dt9770002297
Abstract
The reaction of [Ti(cp)2(CO)2](1)(cp =η-C5H5) with acyl halides RCOCl (R = Me or Ph) gives acyl derivatives of titanium(IV), [Ti(cp)2(COR)Cl]. Under the same conditions, the reaction of (1) with alkyl iodides gives the acyl derivatives [Ti(cp)2(COR)I](R = Me, Et, Pri, or Bus). All the acyl derivatives are characterised by a low CO stretching frequency [ν(CO) at ca. 1 600 cm–1]. X-Ray analysis of [Ti(cp)2(COMe)Cl] shows that the molecule has Cs symmetry with atoms Ti and Cl and the acetyl group lying in the crystallographic mirror plane. The Ti atom has distorted tetrahedral co-ordination, and it interacts strongly with the oxygen of the acetyl group which acts as a bidentate three-electron ligand. This structure explains the observed low CO stretching frequency for the acyl unit. Reaction with MeSO2Cl resulted in insertion of the Ti(cp)2 unit into the S–Cl bond giving [Ti(cp)2(O2SMe)Cl]. Reactions of (1) with iodide, phenanthrene-9,10-quinone. and PPh2Cl are also reported.Keywords
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