Neutron and X-ray Diffraction Studies and DFT Calculations of Asymmetric Bis(silyl) Niobocene Hydrides

The first asymmetric bis(silyl) niobocene hydrides Cp2Nb(SiHMe2)H(SiXMe2) (2: X = F (a), Cl (b), Br (c), I (d)), having interligand interactions Nb−H···Si−X, were prepared by selective halogenation of the Si−H bond in Cp2Nb(SiHMe2)2H. X-ray studies of 2b,c and a combined X-ray/neutron diffraction study of 2b establish a slightly stronger interaction of the niobium-bound hydride with the halosilyl ligand.首个不对称双(硅基)二茂铌氢化物Cp₂Nb(SiHMe₂)H(SiXMe₂)（编号2：X = F(a)、Cl(b)、Br(c)、I(d)），其分子内存在Nb−H···Si−X型配体间相互作用，可通过对Cp₂Nb(SiHMe₂)₂H中的Si−H键进行选择性卤化反应制备得到。针对2b、2c开展X射线衍射研究，并对2b实施X射线与中子衍射联合表征，结果证实与铌键合的氢化物与卤硅基配体之间的相互作用略强。