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

Abstract

In this paper we have reported mono- and dinuclear molybdenum compounds containing doubly bridging pymS (pyrimidine-2-thiolato) and P(Fu)₃{(Fu = (2-furyl)phosphine)} or P(OMe)₃(trimethyl phosphite). One-pot reaction between [Mo(CO)₃(NCMe)₃] and pymSH (pyrimidine-2-thiol) in the presence of P(Fu)₃ in THF at 50 °C gives the previously reported eight coordinate compound [Mo(к²-pymS)₄] (<strong>1</strong>) in 17% yield and two new compounds [Mo(CO)₄(P(Fu)₃)₂] (<strong>2</strong>) and [Mo₂(CO)₄(μ-к²-pymS)₂(P(Fu)₃)₂] (<strong>3</strong>) in 51 and 15% yields, respectively. A similar reaction involving P(OMe)₃furnishes two mononuclear compounds [Mo(CO)₂(κ²-pyS)₂(P(OMe)₃)] (<strong>4</strong>) and [Mo(CO)₄(P(OMe)₃)₂] (<strong>5</strong>) in 20 and 35% yields, respectively. Compounds <strong>2</strong> and <strong>4</strong> are characterized by single-crystal X-ray diffraction analysis in addition to IR, ¹H NMR and ³¹P{¹H} NMR spectroscopic methods.