Reactions of (Me_C)(Me_Si)[(eta_5-C_5H_3)Mo(CO)_3]_2 with Phosphanylalkynes: Rearrangement of Phosphanylalkynes into Phosphido-Substituted Vinylidenyl Ligands by Cleavage of the P-C(alkyne) Bond and Formation of a P-C(alkene) Bond

摘要

This article deals with the thermal reactions of the doubly bridged bis(cyclopentadienyl) dinuclear molybdenum complex (Me2C)(Me2Si)1(eta(5)-C5H3)Mo(CO)(3)](2) (1) with a series of phosphanylalkynes PhnP(C CR)(3-n) (n = 2, 1, 0; R = Ph, Fc). In addition to the complex (Me2C)(Me2Si)[(eta(5)-C5H3)(2)Mo-2-(CO)(4) (mu-eta(2)-eta(2)(perpendicular to)-(RC)-C-1 CR2)] [R-1 = Ph, R-2 = Ph2P, 2; R-1 = Ph, R-2 = Ph2P(O), 4; R-1 = Ph, R-2 = PhP(C CPh), 6; R-1 = Fc, R-2 = PhP(C CFc), 8; and R-1 = Fc, R-2 = PhP(O)(C CFc), 10], in which the phosphanylalkynes acted as disubstituted acetylenes, the P-C(alkyne) bond cleavage and phosphanylalkyne rearrangement products (Me2C)Me2Si)[(eta(5)-C5H3)(2)Mo-2-(CO)(4){mu-eta(1)-C=C (R-1)R-2}] [R-1 = Ph, R-2 = Ph2P, 3; R-1 = Fc, R-2 = Ph2P, 5; R-1 = Ph, R-2 = PhP(C CPh), 7; and R-1 = Fc, R-2 = PhP(C CPh), 9] were also isolated when mono- and bis-(ethynyl)-functionalized phosphanes reacted with 1. Reactions of tris (ethynyl)-functionalized phosphanes with I afforded the phosphanylalkyne-bridged complexes (or/and their oxide) (Me2C)(Me2Si)[(eta(5)-C5H3)(2)Mo-2(CO)(4)(mu-eta(2)-eta(2)(perpendicula r to)- (RC)-C-1 CR2)] [R-1 = Ph, R-2 = P(C CPh)(2), 11a and 11b; R-1 = Ph, R-2 = P(O)(C CPh)(2), 12; and R-1 = Fc, R-2 = P(C CFc)(2), 13]. All the new complexes were fully characterized. X-ray characterization of 3, 5, 6, 7, 11a, 11b, 13, and P(C CFc)(3) are also provided. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)