A Transient Vanadium(III) Neopentylidene Complex. Redox Chemistry and Reactivity of the VCH[superscript t]Bu Functionality
The vanadium(III) bis(neopentyl) complex (PNP)V(CH{sub 2}{sup t}Bu){sub 2} (PNP = N[4-Me-2-(P{sup i}Pr{sub 2})C{sub 6}H{sub 3}]{sub 2}{sup -}), a complex readily prepared from alkylation of (PNP)VCl{sub 2} with 2 equiv of LiCH{sub 2}{sup t}Bu, serves as a precursor to the transient vanadium(III) alkylidene complex '(PNP)V{sub {double_bond}}CH{sup t}Bu'. Two-electron oxidation of the intermediate [(PNP)V{sub {double_bond}}CH{sup t}Bu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)V{sub {double_bond}}CH{sup t}Bu(X) (X = O, S, Se, Te). This family of chalcogenide-alkylidenes has been studied via {sup 51}V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)V{sub {double_bond}}CH{sup t}Bu] and the reactivity of the alkylidene ligand are explored with the substrates N{sub 3}SiMe{sub 3}, N{sub {open_square}}C{sup t}Bu, N{sub 2}, and azobenzene. It was discovered that N{sub {double_bond}}N cleavage of the last substrate can be achieved without oxidation of the metal.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 1005657
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: (3) ; 02, 2009 Vol. 28; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- ENGLISH
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