文摘
The dichlorophosphanyl-substituted ferrocene complexes 1-dichlorophosphanyl-2-N,N-dimethylaminomethyl-3-diphenylphosphanylferrocene (2a) and 1-dichlorophosphanyl-2-N,N-dimethylaminomethyl-3,1′-bis(diphenylphosphanyl)ferrocene (2b) have been prepared by the reaction of phosphorus trichloride with the corresponding lithiated aminoalkylferrocene precursors. The crystal structure of 2a reveals a short N···P distance, which is suggestive of a weak N→P dative bond. Using diethyl chlorophosphite instead of phosphorus trichloride as electrophile gave 1-diethoxyphosphanyl-2-N,N-dimethylaminomethyl-3-diphenylphosphanylferrocene (3a) and 1-diethoxyphosphanyl-2-N,N-dimethylaminomethyl-3,1′-bis(diphenylphosphanyl)ferrocene (3b), respectively. The latter was converted to the corresponding dimethoxy compound 4b by reaction with methanol. Crystal structures of 3 and 4b have been determined. Reduction of 2, 3, and 4b with LiAlH4 or LiAlH4/SiMe3Cl yielded the primary phosphanes 1-diphenylphosphanyl-2-N,N-dimethylaminomethyl-3-phosphanylferrocene (5a) and 1,1′-bis(diphenylphosphanyl)-2-N,N-dimethylaminomethyl-3-phosphanylferrocene (5b). The latter was also structurally characterized by X-ray diffraction.