COMPLEX HALIDES OF THE TRANSITION-METALS .27. REACTIONS OF NITRIC-OXIDE WITH MOLYBDENUM(II) DIMERS CONTAINING METAL-METAL QUADRUPLE BONDS - NEW ROUTE TO MONOMERIC DINITROSYL DERIVATIVES OF MOLYBDENUM

Nitric oxide reacts with the metal-metal bonded dimers Mo2X4L4, where X=Cl or Br and L=PEtPh2, PEt3, or P-n-Bu3, and Mo2X4(LL)2, where X=Cl or NCS and LL=l,2-bis(diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)methane (dppm) in dichloromethane to afford the dinitrosyls of molybdenum, Mo(NO)2X2L2 and Mo(NO)2X2(LL). The cleavage of the Mo-Mo quadruple bond of the starting materials is contrasted with the reaction of carbon monoxide with the rhenium(II) dimers Re2X4(PR3)4 to produce trans-Re(CO)2X2(PR3)2 and the lack of reactivity of Mo2X4(PR3)4 toward this same ligand. © 1979, American Chemical Society. All rights reserved.