Formation of novel ansa-carborane-alkoxide complexes by carbonylation of (C5Me5)(η5-C2B9H 11)TiMe

Xiaohong Bei, Carsten Kreuder, Dale C. Swenson, Richard F. Jordan, Victor G. Young

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The reaction of Cp*(η5-C2B9H11)TiMe (1, Cp* = C5Me5) with CO (0.5-1 atm) in toluene (-78 to 23 °C) yields a 1:4 mixture of Cp*(η51-8-CHMeO-C2B 9H10)Ti (6) and Cp*(η51-4-CHMeO-C2B 9H10)Ti (7), in ca. 90% total NMR yield. Complexes 6 and 7 both contain a linked carborane-alkoxide ligand but differ in the site of attachment of the -CHMeO-linker to the carborane cage. The linker is attached at the central boron of the C2B3 donor ring (B8) in 6 and to a lateral boron (B4 or B7) in 7. The anticipated acyl complex, Cp*-(η5-C2B9H11)TiC(=O)Me (8), was not observed. However, experiments with 13CO show that the -BCHMeO- carbon atoms in 6 and 7 originate from the CO, which implies that 8 is formed first and rearranges to 6 or 7 by net insertion of the acyl carbon into a B-H bond. The molecular structures of 6 and Cp*(η51-4-CHMeO-C2B 9H10)Ti(NCMe) (9) have been determined by X-ray crystallography.

Original languageEnglish (US)
Pages (from-to)1085-1091
Number of pages7
Issue number6
StatePublished - Mar 16 1998

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