Synthesis of cyclopentadienyl ruthenium 4-pyridine and 2-pyrimidine thiolates and their bimetallic group VI metal carbonyls

A simple one pot synthesis of CpRu(P-F)S-4-Py (Cp = eta(5)-C5H5; P-P = dppm (1), dppe (2); Py = pyridine) and CpRu(P-P)S-2-Pym (P-P = dppm (3), dppe (4); Pym = pyrimidine) by the three component reaction of CpRu(PPh3)(2)Cl, thiolate anions and the diphosphine ligand has been accomplished. Complexes 1 and 2 reacted with M(C0)5THE at room temperature to give the new heterobimetallic complexes CpRu(P-P)(mu-4-SPy)(M(CO)(5)) [P-P = dppm (5), dppe (6); M = Cr (a), Mo (b), W (c)]. The corresponding reactions of 3 and 4 with M(CO)(5)THF produced CpRu(P-P)(mu-2-SPym-kappa S-2,N)(M(CO)(4)) (P-P = dPPm (7), dppe (8); M = Cr (a), Mo (b), W(c)). These new complexes have been characterized by spectroscopic methods (FT-IR, H-1 and P-31 NMR) and elemental analysis. The solid-state structures of CpRu(dppm)-4-SPy and CpRu(dppe)-4-SPy have been determined by X-ray crystallography. (C) 2015 Elsevier Ltd. All rights reserved.