κ1-Br adduct [(FPNP)Pt–Cl–Ph]+ (4) or [(FPNP)Pt–Br–Ph]+ (10). Compound 4 rearranges into a C–H splitting product [(FPN(H)P)Pt–C6H4Cl]+ (3f), while 10 slowly reacts by formal transfer of Br atom to Pt. An analogous Cl atom transfer to Pt is observed upon the reaction of 1 with K[B(C6F5)4] in dichloromethane, producing [(FPNP)PtCl][B(C6F5)4] (9a) which features an oxidized FPNP ligand framework. X-Ray diffractometry
该手稿探讨了与未观察到的14电子[(F
PNP)Pt] +瞬态(F
PNP =(4-F-2-(i Pr 2 P)C 6 H 3)2 N)有关的新
化学。可以通过在用作底物的各种溶剂中从(F
PNP)PtOTf(1)用K [B(C 6 F 5)4 ]提取
三氟甲磺酸盐来获得其反应性。和苯,
甲苯 和
氟苯,观察到芳香族C–H键跨N–Pt键的净杂化分裂,没有任何可检测的中间体,从而导致[[ F
PN(H)P)Pt–Ar] +产物(Ar = Ph,3a ; Ar = C 6 H 4 Me,3b(邻位),3c(间位),3d(对位); Ar = o -C 6 H 4 F,3e)。后者可以通过中性(F
PNP)Pt-Ar化合物的质子化来制备。化合物3a–3e不会在80°C的热分解下释放出游离的
芳烃,并且化合物3b / c / d在环境温度下不会相互转化。和
氯苯 和
溴苯,动力学产物是κ 1 -Cl或κ 1