Organometallic Complexes of Benzannelated Phospholyls:Synthesis and Characterization of Benzophospholyl and the First iso-Benzophospholyl Metal Complexes

摘要

A large-scale synthesis of the benzophospholyl (BP) ligand,4,has been developed and employed in the synthesis of a series of manganese and iron complexes.Reaction between Li-BP and FeCp(CO)_2X (X=Br,I) resulted in the formation of [(mu_2-BP)Fe_2Cp_2(CO)_4]X,while reaction of bis(l,1'-benzophospholyl) with [FeCp(CO)_2]_2 gave a mixture of isomers of (mu_2-BP)_2Fe_2Cp_2(CO)_2.The phosphine adduct (BP-Ph)Mn_2(CO)_9 was obtained from BP-Ph and Mn_2(CO)_(10) and converted to (eta~5-BP)Mn(CO)_3 upon reaction with organometallic or organic radicals.A synthesis for phenyl-iso-benzophosphole (iBP-Ph) has been explored.The compound is highly reactive and polymerizes instantaneously and irreversibly.Polymerization of the iBP precursor was avoided in the novel partially hydrogenated derivative iBP-H_2-Ph.Manganese complexes of iBP,5,were obtained by reaction of iBP-H_2-Ph with Mn_2(CO)_(10),resulting in the formation of (eta~5-iBP-H_2)Mn(CO)_3.Reaction of (eta~5-iBP-H_2)Mn-(CO)_3 with DDQ gave (eta~5-iBP)Mn(CO)_3,the first metal complex of iBP.