Preparation of heteronuclear bridging methylene complexes

Abstract

The reactions of the titanacyclobutane complexes (η^5-C_5H_5)_2TiCH_2CRR'CH_2 (la, R = R' = Me; lb, R = Me, R' = Pr) with M-X compounds (M =Ti, Zr, Rh, Ir, Pd, Pt; X = Cl, OMe) have been investigated. The titanacyclobutanes have been found to react as sources of (η^5-C_5H_5)_2TiCH_2, giving (η^5-C_5H_5)_2Ti(μ –CH_2)(μ-X)ML_n (L_n = ancillary ligands) products. Several such complexes have been isolated as crystalline solids; however, only (η^5-C_5H_5_2Ti(μ-CH_2)(μ-X)Rh(η^4-l,5-cyclooctadiene) is stable in solution at 25°C. The complex η^5-C_5H_5)_2iTi(μ-CH_2)(μ-Cl)Ti(η^5-C_5Me_5)Cl was found to react with CO to form the bridging ketene complex (η^5-C_5H_5)_2Ti-μ, η^2(C,O)-(OCCH_2)Ti(η^5-C_5Me_5)Cl_2.

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