6b/6a in CDCl3 at 55 °C. Under the same conditions, the rate of isomerization of 6a to 6b is 4.32 × 10−6 s−1. Isomerization is thought to proceed by an initial attack of a carbonyl group by a pendant phosphine followed by ring opening and a 1,2-phosphine shift. At higher temperatures, chelated complexes with four- and six-membered rings are formed: [(OC)5Wμ-κ1-, κ2-PPh2CH2 (PhPCH2PPh2)W(CO)4 }] 9a, [(OC)5Wμ-κ1-
的[W(CO)反应5 NH 2 PH]的Ph 2 PCH 2 PPhCH 2 PPH 2 [(OC):温和的条件和
化学计量的控制引线下两组连杆异构体的5 W κ 1 - P博士(CH 2 PPH 2)2 }]图6a和[(OC)5 W(κ 1 - P博士2 CH 2 PPhCH 2 PPH 2)]图6b ; [(OC)5 W µ- P Ph 2CH 2 P博士(CH 2 PPH 2)} W(CO)5 ]图7a和[(OC)5 W(μ- P博士2 CH 2 PPhCH 2 P博士2)W(CO)5 ]图7b。异构体6a和6b在平衡状态下存在于溶液中,在55°C下于CDCl 3中对6b / 6a的K = 4.35 。在相同条件下,6a到6b的异构化速率为4.32×10 -6 s -1。据认为,异构化是通过膦基侧基首先攻击羰基,然后开环和1,2-膦移位而进行的。在较高温度下,螯合络合物与四和六元环形成:[(OC)5