Synthesis, characterisation, reactivity and stereochemical studies of heterobimetallic complexes containing an orthometallated cyclopentadienylphosphine bridge

Abstract

The heterobimetallic diastereoisomer complexes [X(η⁵-C₅H₅)Mo{(η⁵ -C₅H₄)PPh(o-C₆H₄ )}M(CO)₅] (X = Cl 1 and 1′ or I 2 and 2′; M = Cr a, Mo b or W c) containing an orthometallated cyclopentadienylphosphine bridge have been prepared and characterised. They were obtained by reaction of Li[M(CO)₅(PPh₂)] and the corresponding metallocene dichloride in tetrahydrofuran. The crystal structures of 1a and 2c showed that the η⁵-C₅H₄PPh[M(CO)₅]C ₆H₄ fragment chelates the Mo. Similarly, methylated complexes 3 were prepared when [Mo(η⁵-C₅H₄Me)₂Cl ₂] was used as metallocene dichloride; the 1,3 regioselectivity of these reactions has been assigned on the basis of  ¹H and  ³¹P NMR data. Compound 1c reacted with LiAlH₄ to give a dihydride molybdenocene complex [H(η⁵-C₅H₅)Mo(η⁵-C ₅H₄PPh₂)HW(CO)₄]. Alkylated diastereoisomers [R(η⁵-C₅H₅)Mo{(η⁵ -C₅H₄)PPh(o-C₆H₄ )}M(CO)₅] (R = Me or Et) were obtained by reaction of 1c with a Grignard reagent; cleavage of the Mo–Me bond with hydrochloric acid has been found to occur with retention of configuration.

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