Nucleophilic discrimination and the trans effect. The kinetics of displacement of X from trans-[Pt(L)(X)Cl2] n? (L = Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3; X = Cl, n= 1; X = MeOH, n= 0) by neutral and anionic nucleophiles
作者:Martin L. Tobe、Andrew T. Treadgold、Lucio Cattalini
DOI:10.1039/dt9880002347
日期:——
The kinetics of the reaction trans-[Pt(L)(X)Cl2]n–+ L′→trans-[Pt(L)(L′)Cl2]n′–+ X (X = Cl–, n= 1, L = Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3, L′= pyridine (py), Me2S, Et2S, PPh3, Me2SO, thiourea (tu), or NNN′N′-tetramethylthiourea (tmtu), n′= 0; L′= Cl–, Br–, I–, or SCN–, n′= 1; X = MeOH, n= 0, L′= Cl–, Br–, I–, or SCN–, n′= 1) have been studied in 95% methanol + 5% water at 25 °C. The second-order
该反应的动力学反式- [铂(L)(X)氯2 ]正+ L'→反式- [铂(L)(L')氯2 ] -N' - + X(X =氯- ,Ñ = 1,L =我2 SO,等2 S,PME 3,宠物3,PPH 3,或ASET 3,L'=吡啶(PY)中,Me 2 S,等2 S,PPH 3中,Me 2 SO,硫脲(TU),或NNN ' ñ '-tetramethylthiourea(tmtu),ñ '= 0; L'=氯-,溴-,I –或SCN –,n '= 1;X = MeOH,n = 0,L'= Cl –,Br –,I –或SCN –,n '= 1)已在25%的95%甲醇+ 5%水中进行了研究。阴离子底物的二级速率常数k 2不遵循通常的依赖关系,即n 0 Pt',阴离子亲核试剂的反应性比预期的要小得多。基于[Pt(Et 3 As)Cl 3 ]的新亲核标度–作为标准底物,确实给出了所有阴离子底物的线性关系。