iminophosphine. Complexes 1a−g react with methyl iodide to give Rh(III) methyl or acetyl products. For complexes 1a,d,f,g the reactions result in equilibria between the methyl complexes [Rh(CO)(PNAr)I2Me] (2) and acetyl complexes [Rh(PNAr)(COMe)I2] (3), whereas the reactions of 1b,c,e gave only the acetyl products [Rh(COMe)I2(PNAr)] (3b,c,e). Migratory CO insertion is promoted for systems in which
通过[Rh(CO)2 I] 2与亚
氨基
膦配体Ph 2 PC的反应,制备了一系列Rh(I)
碘羰基配合物[Rh(CO)I(
PN Ar)](1a - g)。6 H 4 -2-CH NAr(
PN Ar ; Ar = C 6 H 5(a),2,6-Me 2 C 6 H 3(b),2,6- i Pr 2 C 6 H 3(c) ,2-EtC 6 H 4(d),2-MeOC 6 H 4(e),4-MeOC 6 H 4(f),3,5-(CF 3)2 C 6 H 3(g))。对于13个CO标记的1b,相对较小的2 J CP偶联(12 Hz)显示,CO
配体与亚
氨基膦的P-给体原子顺式排列。配合物1a - g与
碘甲烷反应生成Rh(III)甲基或乙酰基产物。对于复合物1a,d,f,g该反应导致甲基络合物之间的平衡的[Rh(CO)(
PN的Ar)我2本人](2)和乙络合物的[Rh(
PN的Ar)(COME)我2 ](3)