Preparation and characterization of two high oxidation state molybdenum dinitrogen complexes: (MoCp sup * Me sub 3 ) sub 2 (. mu. -N sub 2 ) and (MoCp sup * Me sub 3 )(. mu. -N sub 2 )(WCp prime Me sub 3 )
- Massachusetts Institute of Technology, Cambridge (USA)
(MoCp{sup *}Cl{sub 4}){sub 2} (Cp{sup *} = C{sub 5}Me{sub 5}) is alkylated by MeMgCl in tetrahydrofuran to give red microcrystalline MoCp{sup *}Me{sub 4} in {approximately}70% yield. MoCp{sup *}Me{sub 4} reacts with 1 equiv of HOSO{sub 2}CF{sub 3} in ether to give purple microcrystalline MoCp{sup *}Me{sub 3}(OSO{sub 2}CF{sub 3}) in {approximately}85% yield. Triflate can be displaced readily from MoCp{sup *}Me{sub 3}(OSO{sub 2}Cf{sub 3}) by adding LiOR (OR = pentafluorophenoxide, 2,6-diisopropylphenoxide, 2,6-dimethoxyphenoxide, 2,4,6-trimethoxyphenoxide, 2,6-dimethyl-4-methoxyphenoxide, and catecholate) in ether to yield complexes of the type MoCp{sup *}Me{sub 3}(OR) (MoCp{sup *}Me{sub 2}(cat) in the case of catecholate) in 50-80% yield. The complexes can be oxidized chemically (with the exception of OR = pentafluorophenoxide and catecholate) by (FeCp{sub 2})(PF{sub 6}) in methylene chloride to give complexes of the type (MoCp{sup *}Me{sub 3}(OR))(PF{sub 6}) as orange-brown microcrystalline powders in 80-90% yield. Addition of 3 equiv of hydrazine to (MoCp{sup *}Me{sub 3}(OR))(PF{sub 6}) in ether provides (MoCp{sup *}Me{sub 3}){sub 2}({mu}-N{sub 2}) in low yield after purification by filtration through alumina and recrystallization from ether. (MoCp{sup *}Me{sub 3}){sub 2}({mu}-N{sub 2}) belongs to the space group P2{sub 1}/n.
- OSTI ID:
- 6611898
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 112:11; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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