Molybdenum complexes bearing pyrimidine-2-thiolato (pymS) and tertiary phosphine ligands

Abstract

In this paper we report mono- and dinuclear molybdenum complexes containing doubly bridging pymS and tertiary phosphine ligands PFu 3 or P(OMe) 3. One-pot reaction between [Mo(CO) 3 (NCMe) 3 ] and pymSH in the presence of tris(2-furyl)phosphine (PFu 3 ) in THF at 50 ˚C gives the previously reported eight coordinate compound [Mo( к 2 -pymS) 4 ] ( 1) in 17% yield and two new compounds [Mo(CO) 4 (PFu 3 ) 2 ] ( 2 ) and [Mo 2 (CO) 4 (μ- к 2 -pymS) 2 (PFu 3 ) 2 ] ( 3 ) in 51 and 15% yields, respectively. A similar reaction involving P(OMe) 3 furnishes two mononuclear complexes [Mo(κ 2 -pyS) 2 (CO) 2 {P(OMe) 3 }] ( 4 ) and [Mo(CO) 4 {P(OMe) 3 } 2 ] ( 5 ) in 20 and 35% yields, respectively. Complexes 2 and 4 were characterized by single-crystal X-ray diffraction analysis in addition to IR, 1 H NMRand 31 P{ 1 H} NMR spectroscopic methods.