Functionalization and reactivity of a vanadium carbamate complex

INOR 37

Jared S. Silvia, jssilvia@mit.edu and Christopher C. Cummins, ccummins@mit.edu. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Building 6-327, Cambridge, MA 02139
The vanadium complex [Na(THF)2][O2CNV(N[t-Bu]Ar)3] (1, Ar = 3,5-Me2C6H3) forms quantitatively from the reaction of carbon dioxide with the vanadium nitrido- complex Na[NV(N[t-Bu]Ar)3]. Complex 1 displays nucleophilic properties and reacts with a variety of electrophiles to functionalize the carbamate group. As an example, the trimethylsilyl capped species Me3SiO2CNV(N[t-Bu]Ar)3 forms from the reaction of 1 with trimethylsilyl triflate. The carbamate functional group can also be converted to the isocyanate if the electrophile can additionally act as a one-electron reducing agent. For example, the vanadium complex (TfO)V(N[t-Bu]Ar)3 (Tf = SO2CF3) is converted to the known oxo-vanadium trisanilide complex upon treatment with 1. Presented is a discussion of the functionalization reactions, the reactivity of the products, and efforts to deoxygenate the carbamate group in a productive manner.
 

Synthetic Coordination Chemistry
8:30 AM-12:30 PM, Sunday, August 19, 2007 BCEC -- 213, Oral

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007