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

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.