SYNTHESES AND REACTIONS OF HALOPHOSPHINE COMPLEXES OF GROUP 7 TRANSITION METALS (Mn AND Re)

Abstract

Abstract The photochemical reactions of the “piano stool” complexes CpMn(CO)3, CpRe(CO)3, and Cp∗ Mn(CO)3 (Cp∗ = η5-C5Me5) with the bidentate halophosphine ligand 1,2-bis(dichlorophosphino)ethane, Cl2PCH2CH2PCl2 (dcpe), gave the chelate complexes CpMn(CO)dcpe (1), CpRe(CO)dcpe (2), and Cp∗ Mn(CO)dcpe (3), respectively. Reactions of the dihalophosphine complexes 1,2 with excess F1- and MeO1- gave the substituted compounds CpM(CO)(R2PCH2CH2PR2) (4, M = Mn, R = F; 5, M = Mn, R = MeO; 6, M = Re, R = F). The ligand-bridged bimetallic complexes [CpM(CO)2](μ-dcpe)[(CO)2M′Cp] (9, M,M′ = Mn; 10, M,M′ = Re; 11, M = Mn, M′ = Re) were prepared by treatment of the dangling compounds CpM(CO)2 dcpe (7, M = Mn; 8, M = Re) with the solvento complex CpM′(CO)2(THF) (M′ = Mn or Re). The crystal structures of 1, 2, and 6 were determined by single crystal X-ray structure analyses. 1: monoclinic, P21/c, a = 12.008(2) A, b = 15.685(2) A, c = 14.980(2) A, β = 91.01(2)°, V = 2821.0(6) A3, Z = 8, R = 0.046; 2: monoclinic, P21/c, a ...