Pentacarbonyl(diethylaminocarbyne)chromium tetrafluoroborate, [(CO)5− CrCNEt2]BF4 (I), reacts with PPh3 with substitution of CO and formation of trans-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium tetra-fluoroborate, trans-[PPh3(CO)4CrCNEt2]BF4 (III). Substitution of CO by PPh3 in neutral trans-tetracarbonyl(halo)(diethylaminocarbyne)chromium complexes, trans-X(CO)4CrCNEt2 (IVa: X =
五羰基(diethylaminocarbyne)
铬四
氟硼酸盐,[(CO)5- CrCNEt 2 ] BF 4(I),进行反应与PPH 3与CO的取代和形成的反式-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium四
氟硼酸盐,反式- [PPH 3( CO)4 CrCNEt 2 ] BF 4(III)。PPh 3在中性反式-四羰基(卤)(
二乙基氨基碳炔)
铬络合物中反式-X(CO)4 CrCNEt 2取代CO(IVa:X = Br,IVb:X = I),导致可逆反应生成相应的三羰基配合物,mer -X(PPh 3)(CO)3- CrNEt 2(V),PPh 3占据顺式位置卡宾
配体。PPh 3大量过量时,两个反应均遵循一阶速率定律。这以及激活参数(ΔH ≠= 104–113 kJ mol -1,ΔS ≠= 64–71 J mol