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简单的锇起始物OsHCl(PPh_3)_3(1)或OsCl_2(PPh_3)_3(2)与3-氯-3-甲基-1-丁炔反应可分别得到锇的烯基卡拜配合物OsHCl_2(≡CCH=CMe_2)(PPh_3)_2(3)和OsCl_3(≡CCH=CMe_2)(PPh_3)_2(4).化合物3与二苯基(苯乙炔基)膦反应可转化为三个二苯基(苯乙炔基)膦配位的锇烯基卡宾配合物OsCl_2(=CHCH=CMe_2)(Ph_2PC≡CPh)_3(5),而化合物4与二苯基(苯乙炔基)膦反应得到膦配体取代产物OsCl_3(≡CCH=CMe_2)(Ph_2PC≡CPh)_2(6).二苯基(苯乙炔基)膦配体较弱的供电子能力及较小的空间位阻是促成化合物3发生锇上的原子氢配体到卡拜碳的1,2-迁移而转化为卡宾配合物5的原因.
The reaction of 3-chloro-3-methyl-1-butyne with the simple osmium precursor OsHCl (PPh_3) _3 (1) or OsCl_2 (PPh_3) _3 (2) (≡CCH = CMe_2) (PPh_3) _2 (3) and OsCl_3 (≡CCH = CMe_2) (PPh_3) _2 (4) The reaction of compound 3 with diphenyl (phenylethynyl) phosphine can be converted into three diphenyl (Phenylethynyl) phosphine, osmium alkenyl carbene complex OsCl_2 (= CHCH = CMe_2) (Ph_2PC≡CPh) _3 (5), while compound 4 reacted with diphenyl (phenylethynyl) phosphine to obtain phosphine ligand The substitution product OsCl_3 (≡CCH = CMe_2) (Ph_2PC≡CPh) _2 (6). The weaker electron-donating ability and less steric hindrance of diphenyl (phenylethynyl) Of the atomic hydrogen ligands to the 1,2-carbon carbene carbon into carbene complex 5 reasons.