Co-ordination chemistry of 2,6-diphenylthiophenol. The syntheses and X-ray crystal structures of some molybdenum and rhodium complexes with σ- or η6-phenyl–metal interactions

Abstract

Reaction of [MoCl₂(CO)₄] with the 2,6-diphenylthiophenolate anion (dpt) gives the complex [Mo(η⁶-dpt)(dpt)(CO)], with one thiol phenyl substituent η⁶-bonded to the molybdenum. Crystal data: space group P2₁/c, with a= 13.939(3), b= 10.548(3), c= 20.863(5)Å, β= 106.88(1)° and Z= 4. The η⁶arene ligand is labile and is reversibly replaced by CO. Replacement of this ligand also occurs with 2,2′-bipyridyl(bipy),1,10-phenanthroline (phen), and 1,2-bis(diphenylphosphino)ethane (dppe) to give the dicarbonyl complexes [Mo(dpt)₂(CO)₂L](L = bipy or phen) or the monocarbonyl complex [Mo(dpt)₂(CO)(dppe)]. The X-ray crystal structure of the bipy derivative and the mechanism of its formation is discussed. Crystal data: space group P2₁/c with a= 10.567(3), b= 22.843(5), c= 18.341(3)Å, β= 105.2(2)° and Z= 4, Reaction of RhCl₃ with dpt gave the dinuclear species [Rh₂{µ-SC₆H₃(C₆H₄)-2-Ph-6}₂(dpt)₂(NCMe)₂]. An X-ray crystal structure reveals that each bridging thiolate ligand is also σ-bonded to rhodium [Rh–C 2.016(8)Å]via one of the phenyl carbons of the thiolate substituents. Crystal data: space group P2₁/n, a= 11.991(2), b= 20.426(4), c= 15.910(4)Å, β= 90.42(1) and Z= 2.