179235-22-4

Basic information

• Product Name: W(CO)3(NO)((C₆H₅)2PCH₂)2⁽¹⁺⁾
• CAS NO: 179235-22-4
• Molecular Weight: 696.311
• Mol File: 179235-22-4.mol
• Article Data: 1

Chemical Properties

• CAS DataBase Reference: W(CO)3(NO)((C₆H₅)2PCH₂)2⁽¹⁺⁾(CAS DataBase Reference)
• NIST Chemistry Reference: W(CO)3(NO)((C₆H₅)2PCH₂)2⁽¹⁺⁾(179235-22-4)
• EPA Substance Registry System: W(CO)3(NO)((C₆H₅)2PCH₂)2⁽¹⁺⁾(179235-22-4)

Safety Data

• Hazardous Substances Data: 179235-22-4(Hazardous Substances Data)

Upstream product

• 16921-91-8 nitrosyl hexafluorophosphate 
• 29890-05-9 tetracarbonyl-1,2-bis(diphenylphosphino)ethane-tungsten(0) 

Relevant articles and documents

Reaction pathways of geometrically constrained 17-electron cis-[M(CO)4(L-L)]+ cations (M = Cr, Mo, W; L-L = bidentate ligand)

Oxidation of cis-M(CO)4(L-L) (where M = Cr, Mo, W and L-L is a bidentate ligand with P, As, or Se donor atoms) leads to generation of geometrically constrained 17-electron cations cis-[M(CO)4(L-L)]+, which cannot lower their energy by isomerization to the trans+ configuration, as is the case with [M(CO)4L2]+ and related complexes (L = monodentate P or As ligand). In this work, a marked contrast in reaction pathways between geometrically constrained compounds and other classes of compounds is shown to exist. The relative stability of cis-[Cr(CO)4(dpm)]+ in dichloromethane allows complete characterization of its chemical and electrochemical behavior; it undergoes photocatalytic reduction, substitution, redox, and disproportionation reactions, all of which regenerate Cr(CO)4(dpm). Other cis-[Cr(CO)4(L-L)]+ species are much less stable. The voltammetric oxidations (scan rates 50-500 mV s-1) of Mo(CO)4(L-L) (L-L = dpe, dpmSe) are very unusual. While these species approach chemical reversibility at ambient temperatures in dichloromethane, anomalous temperature dependence leads to the observation of complete chemical irreversibility at -78°C and the concomitant appearance of a new reduction response, well removed from the potential of the reversible process. In the presence of Cl-, PPh3, or L-L the one-electron voltammetric response is converted into an irreversible two-electron process (L-L = dpe) or an irreversible one-electron process (L-L = dpmSe). Other molybdenum and tungsten complexes give chemically irreversible one-electron oxidative voltammetric responses in both dichloromethane and acetonitrile. In acetonitrile, a second one-electron-oxidation process may be observed at very positive potentials. Reaction of cis-M(CO)4(L-L) with NOPF6 produces [M(CO)3NO(L-L)]+ rather than cis-[M(CO)4(L-L)]+. Mechanisms for the chemical and electrochemical oxidation processes are presented in terms of pathways that allow a lowering of energy associated with the formation of 17-electron geometrically constrained cis-[M(CO)4(L-L)]+ cations.