Cleavage of hydrazine and 1,1-dimethylhydrazine by dinuclear tantalum hydrides: formation of imides, nitrides, and N,N-dimethylamine.
The complexes (RPh[NPN]Ta)2(mu-H)4 (RPh[NPN] = RP(CH2SiMe2NPh)2) activate molecular nitrogen to give (RPh[NPN]Ta)2(mu-eta1-eta2-N2)(mu-H)2; however, addition of hydrazine to (CyPh[NPN]Ta)2(mu-H)4 promotes cleavage of the N-N bond and N-H activation to give the bridging bisimide complex (CyPh[NPN]Ta)2(mu-H)2(mu-NH)2. Substitution of the phosphine substituent from cyclohexyl to phenyl allows for characterization of (PhPh[NPN]Ta)2(mu-H)2(mu-NH)2 crystallographically. Addition of the substituted hydrazine Me2NNH2 results in formation of a mono(nitride) complex, (RPh[NPN]Ta)2(mu-H)3(mu-N). The N-N bond has again been cleaved, but the second nitrogen atom has been functionalized and ejected as Me2NH.
Shaver
Michael P
MP
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1.
Fryzuk
Michael D
MD