Radhakrishna Latchupatula, Pandey Madhusudan K, Balakrishna Maravanji S
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay Powai Mumbai 400076 India
RSC Adv. 2018 Jul 18;8(45):25704-25718. doi: 10.1039/c8ra04086a. eCollection 2018 Jul 16.
The reaction of 1-(2-bromophenyl)-4-phenyl-1-1,2,3-triazole (1) with PhPCl yielded bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)phenyl)-4-phenyl-1-1,2,3-triazole (2). Bisphosphine 2 exhibits ambidentate character in either the κ-P,N or κ-P,P coordination mode. Treatment of 2 with [M(CO)(piperidine)] (M = Mo and W) yielded κ-P,N and κ-P,P coordinated Mo and W complexes [M(CO)(2)] [M = W-κ-P,N (4); Mo-κ-P,P (5); W-κ-P,P (6)] depending on the reaction conditions. Formation and stability of κ-P,P coordinated Mo and W complexes were assessed by time dependent P{H} NMR experiments and DFT studies. The complex 4 on treatment with [AuCl(SMe)] afforded the hetero-bimetallic complex [μ-PN,P-{-PhP(CH){1,2,3-NC(Ph)C(PPhAuCl)}-κ-P,N}W(CO)] (7). The 1 : 1 reaction between 2 and [CpRu(PPh)Cl] yielded [(η-CH)RuCl{-PhP(CH){1,2,3-NC(Ph)C(PPh)}}-κ-P,P] (8), whereas the similar reaction with [Ru(η--cymene)Cl] in a 2 : 1 molar ratio produced a cationic complex [(η--cymene)RuCl{-PhP(CH){1,2,3-NC(Ph)C(PPh)}}-κ-P,N]Cl (9). Similarly, treatment of 2 with [M(COD)(Cl)] (M = Pd and Pt) in a 1 : 1 molar ratio yielded Pd and Pt complexes [{-PhP(CH){1,2,3-NC(Ph)C(PPh)}-κ-P,P}PdCl] (10) and [{-PhP(CH){1,2,3-NC(Ph)C(PPh)}-κ-P,P}PtCl] (11). The reaction of 2 with 2 equiv. of [AuCl(SMe)] afforded [AuCl{-PhP(CH){1,2,3-NC(Ph)C(PPh)}}-μ-P,P] (12). Most of the complexes have been structurally characterized. Palladium complex 10 shows excellent catalytic activity towards Cu-free Sonogashira alkynylation/cyclization reactions.
1-(2-溴苯基)-4-苯基-1,2,3-三唑(1)与PhPCl反应生成双膦5-(二苯基膦基)-1-(2-(二苯基膦基)苯基)-4-苯基-1,2,3-三唑(2)。双膦2在κ-P,N或κ-P,P配位模式下表现出双齿特性。用[M(CO)(哌啶)] (M = Mo和W)处理2，根据反应条件生成了κ-P,N和κ-P,P配位的Mo和W配合物[M(CO)(2)] [M = W-κ-P,N (4); Mo-κ-P,P (5); W-κ-P,P (6)]。通过时间相关的P{H} NMR实验和DFT研究评估了κ-P,P配位的Mo和W配合物的形成和稳定性。配合物4用[AuCl(SMe)]处理得到异双金属配合物[μ-PN,P-{ -PhP(CH){1,2,3-NC(Ph)C(PPhAuCl)}-κ-P,N}W(CO)] (7)。2与[CpRu(PPh)Cl]的1:1反应生成[(η-CH)RuCl{-PhP(CH){1,2,3-NC(Ph)C(PPh)}}-κ-P,P] (8)，而与[Ru(η-对异丙基苯)Cl]以2:1摩尔比进行的类似反应生成阳离子配合物[(η-对异丙基苯)RuCl{-PhP(CH){1,2,3-NC(Ph)C(PPh)}}-κ-P,N]Cl (9)。同样，2与[M(COD)(Cl)] (M = Pd和Pt)以1:1摩尔比反应生成Pd和Pt配合物[{ -PhP(CH){1,2,3-NC(Ph)C(PPh)}-κ-P,P}PdCl] (10)和[{ -PhP(CH){1,2,3-NC(Ph)C(PPh)}-κ-P,P}PtCl] (11)。2与2当量的[AuCl(SMe)]反应得到[AuCl{-PhP(CH){1,2,3-NC(Ph)C(PPh)}}-μ-P,P] (12)。大多数配合物已通过结构表征。钯配合物10对无铜的Sonogashira炔基化/环化反应表现出优异的催化活性。
