Dinitrogenvanadates(–<scp>I</scp>): synthesis, reactions and conditions for their stability
作者:Hartmut Gailus、Glaus Woitha、Dieter Rehder
DOI:10.1039/dt9940003471
日期:——
Reduction of [VCl3(thf)(3)] by Na or Li (M) in the presence of phosphines (L(m)) and N-2 yielded the complexes Na[V(N-2)(n)(PMe(2)Ph)(6-n)] (n = 1 or 2), M[V(N-2)(n)L(4-n)(2)] [n = 1 or 2, L(2) = Me(2)PCH(2)CH(2)-PMe(2) (dmpe) or Ph(2)PCH(2)CH(2)PPh(2)], Na[V(N-2)(dmpe)L(3)] L(3) = PhP[(CH2)(2)PPh(2)](2), MeP[(CH2)(3)PMe(2)](2) (bdmpm) or MeP[(CH2)(3)PEt(2)](2)} and Na[V(N-2)(2)L(4)] L(4) = P[(CH2)(2)PPh(2)](3), P[(CH2)(3)PMe(2)](3) or P[(CH2)(3)PEt(2)](3)}. Generally, the complexes are labile, with a maximum stability for cis- and trans-M[V(N-2)(2)(dmpe)(2)]. In the presence of CO or CNBu(t), N-2 is replaced by these ligands. The compounds have been characterized by their v(NN) pattern and by V-51, Na-23 and Li-7 NMR spectroscopy The V-51 NMR spectra exhibit well resolved multiplets. All spectroscopic data, in particular Li-7 NMR of cis-and trans-[Li(thf)(x)][V(N-2)(2)(dmpe)(2)] in tetrahydrofuran, are indicative of close contact ion-pair interaction of the kind V-N=N ... M(+). The potassium ion and large cations such as [NEt(4)](+) do not provide stable complexes, and complexation of Li+ and Na+ by crown ethers leads to immediate decomposition of the N-2 complexes. The reductive protonation of part of the co-ordinated N-2 to NH4+ (plus small amounts of N2H5+) is discussed in terms of similar reactivity features to the analogous complexes, and in the context of these N-2 complexes as functional models for nitrogenases. The compound [V-2(bdmpm)(2)Cl-3], isolated as an intermediate product of the reduction of VCl3 reacted with LiNHNH2 to yield ammonia.