Treatment of the mononuclear alkylidyne complex [WCC6H4Me-4(CO)2(η-C5H5)] with one equivalent of the bidentate phosphine C6H4(PH2)2â1,2 affords the metalla-phosphine complex [WÏ,η3-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)(η-C5H5)] which has an unused lone pair of electrons on the central phosphorus atom of the chelate ring and which undergoes P-methylation and, like a conventional PR3 ligand, will substitute CO ligands in transition metal complexes; the structures of the complexes [WÏ,η3-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)(η-C5H5)], [WlC6H4(PH2)(PMe}CO}CH2C6H4Me-4})-1,2}(CO)(η-C5H5)]·(1/2C4H8O), and [WCo3(η3-CR)µ-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)9(η-C5H5)](R = H or Me) have been determined by single crystal X-ray diffraction studies.
将单核烷基炔配合物[WC Me-4(CO)2(δ--
C5H5)]与一个当量的双齿膦
C6H4(PH2)2â1,2进行处理,可得到
金属-膦配合物[WÏ,δ-3- (PH2)(PCOH}CH Me-4})-1、2}(CO)(δ-- )],它在螯合环的中心
磷原子上有一个未使用的孤对电子,会发生 P-甲基化反应,就像传统的 PR3
配体一样,可以替代过渡
金属配合物中的 CO
配体;络合物[WÏ,δ-3- (PH2)(PCOH}CH Me-4})-1,2}(CO)(δ-- )]、[Wl (PH2)(PMe}CO}
CH2 Me-4})-1,2}(CO)(δ-- )]Â-(1/2C4H8O)的结构、和[WCo3(δ-3-CR)µ- (PH2)(PCOH}CH Me-4})-1,2}(CO)9(δ-- )](R = H 或 Me)已通过单晶 X 射线衍射研究确定。