Photo-and-Thiol-Driven Trans Insertion of Phenylacetylene into H−Pt Bonds
摘要:
The photo-and-thiol-driven trans insertion of phenylacetylene into H-Pt bonds of Pt(X)(H)(PPh3)2 (X = SAr, Cl, Br, and I) took place to afford Pt[(Z)-C(H)=CH(Ph)](X)(PPh3)2 in good yields.
Gaft, Yu. L.; Ustynyuk, Yu. A.; Borisenko, A. A., Russian Journal of Inorganic Chemistry, 1983, vol. 28, p. 1266 - 1270
作者:Gaft, Yu. L.、Ustynyuk, Yu. A.、Borisenko, A. A.、Kuznetsov, N. T.
DOI:——
日期:——
Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands
作者:Stefanus Otto、Ebrahiem Botha、Andreas Roodt
DOI:10.5562/cca3344
日期:——
direct and solvent assisted pathways for 3 were determined as ∆H≠ = 60.4 ± 1.4 and 53.7 ± 0.3 kJ mol−1, and ∆S≠ = −78 ± 4 and −142 ± 1 J mol−1 K−1. A significant more than four orders-of-magnitude reactivity range was observed. Crystal structures of trans-[PtMeCl(PPh2Fc)2].2CHCl3.2H2O, trans-[PtMeClP(NMe2)3}2], cis-[PtMeCl(Ph2PFcPPh2)].2CHCl3 and trans-[PtHCl(PPh3)2].CH3OH are reported.
在一系列铂(II)反式[PtRCl(L)2]络合物(R = Me: L = PPh3,1; PPh2Fc,2; P(NMe2)3,3; AsPh3,5; As(4-Me-Ph)3,6; R = H:L = PPh3,7)和顺式[PtMeCl( Ph2PFcPPh2)],4.反应遵循正常的激活方式,但所有步骤均存在平衡,直接取代途径k12的速率常数为(9.1±1.0)×10−4,0,(1.389) ±0.016)×10−2,(1.51±0.15),(2±4)×10−3,(2.79±0.04)×10−2和0 mol−1 dm3 s-1在298 K下分别为1至7 。还确定了溶剂辅助途径的相应的二级速率常数k13'。3个直接和溶剂辅助途径的活化参数确定为∆H≠= 60.4±1.4和53.7±0.3 kJ mol-1,∆S≠= −78±4和-142±1 J mol−1 K -1。观察到明显超过四个数
Photo-and-Thiol-Driven Trans Insertion of Phenylacetylene into H−Pt Bonds
The photo-and-thiol-driven trans insertion of phenylacetylene into H-Pt bonds of Pt(X)(H)(PPh3)2 (X = SAr, Cl, Br, and I) took place to afford Pt[(Z)-C(H)=CH(Ph)](X)(PPh3)2 in good yields.