Khalimon Andrey Y, Farha Philip M, Nikonov Georgii I
Department of Chemistry, Brock University, 500 Glenridge Ave., St. Catharines, ON L2S 3A1, Canada.
Dalton Trans. 2015 Nov 21;44(43):18945-56. doi: 10.1039/c5dt02945g.
Imido-hydrido complexes (ArN)Mo(H)(Cl)(PMe3)3 (1) and (ArN)Mo(H)2(PMe3)3 (2) (Ar = 2,6-diisopropylphenyl) catalyse a variety of hydroboration reactions, including the rare examples of addition of HBCat to nitriles to form bis(borylated) amines RCH2N(BCat)2. Stoichiometric reactivity of complexes 1 and 2 with nitriles and HBCat suggest that catalytic reactions proceed via a series of agostic borylamido and borylamino complexes. For complex 1, catalysis starts with addition of nitriles across the Mo-H bond to give (ArN)Mo(Cl)(N[double bond, length as m-dash]CHR)(PMe3)2; whereas for complex 2 stoichiometric reactions suggest initial addition of HBCat to form the agostic complex Mo(H)2(PMe3)3(η(3)-NAr-HBcat) (16).
亚胺基氢配合物(ArN)Mo(H)(Cl)(PMe₃)₃ (1) 和(ArN)Mo(H)₂(PMe₃)₃ (2) (Ar = 2,6-二异丙基苯基) 催化多种硼氢化反应，包括HBCat与腈加成形成双(硼化)胺RCH₂N(BCat)₂这种罕见的例子。配合物1和2与腈及HBCat的化学计量反应表明，催化反应通过一系列agostic硼基氨基和硼基胺基配合物进行。对于配合物1，催化作用始于腈通过Mo-H键加成生成(ArN)Mo(Cl)(N=CHR)(PMe₃)₂；而对于配合物2，化学计量反应表明首先是HBCat加成形成agostic配合物Mo(H)₂(PMe₃)₃(η(3)-NAr-HBcat) (16)。
