A novel mixed valence tetranuclear nitrosyl complex bridged by tetraoxomolybdate

Abstract The reaction of the molybdenum–dinitrosyl complexes with PPh 3 , using 2-pyrimidinethiolate (pymt) or 2-pyridinethiolate (pyt) as a thiolate ligand, was found to produce a dinuclear complex [{(ON)MoL 2 } 2 (μ-OH) 2 ] ( 1 ) (L = pymt or pyt) and Ph 3 PO. In addition, the first reported example of a mixed valence molybdenum–nitrosyl tetranuclear complex, [Ph 3 POH] 2 [{(ON)Mo(pymt) 2 } 2 (μ-MoO 4 ) 2 ] ( 2 ), was produced by the reaction of 1(pymt) with Ph 3 PO. This is the first published nitrosyl complex containing both tetraoxomolybdate and thiolato ligands. The molybdenum and bridging oxygen atoms formed a novel eight-membered ring with a central porous structure.