Rhodium(I) and iridium(I) complexes with bidentate N, N and P, N ligands as catalysts for the hydrothiolation of alkynes
Rhodium(I) and iridium(I) complexes with bidentate N, N and P, N ligands as catalysts for the hydrothiolation of alkynes
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DOI：
10.1039/b303774f
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发表时间：
2003-01-01
影响因子：
4
通讯作者：
Turner, P
中科院分区：
文献类型：
--
作者：
Burling, S;Field, LD;Turner, P
含双（1-甲基咪唑-2-基）甲烷，bim，[M（bim）（CO）（2）] BPh 4（M=Ir（1），Rh（2）），双（吡唑-1-基）甲烷，bpm，[M（bpm）（CO）（2）] BPh 4（M=Ir（3），Rh（4））的铱（I），铑（I）阳离子配合物已被证明能有效地催化苯硫酚与一系列炔的区域选择性加成反应。类似的阳离子和中性Ir（I），Rh（I）与新型混合P，N-给体双齿配体1-（2-二苯基膦基）乙基吡唑，PyP（5），[M（PyP）（COD）] BPh 4（M=Ir（6），Rh（7），COD= 1，5-环辛烷）; [Rh（PyP）（COD）] BF 4（8）; [Ir（PyP）（CO）（2）] BPh 4（9）; [Rh（PyP）（CO）（2）] BF 4（10）;合成了[M（PyP）（CO）Cl]（M=Ir（11），Rh（12）），并用NMR进行了表征。用单晶X射线衍射分析测定了化合物（6）、（7）、（11）和（12）的固态结构。与具有N，N-给体配体的类似配合物（1）-（4）相比，具有混合的P，N-给体配体PyP的金属配合物（9）-（12）在大多数情况下更有效地促进炔的氢硫醇化。铱配合物比铑类似物更有效地促进炔的氢硫代反应。阳离子配合物（9）和（10）作为炔的氢硫醇化的催化剂比它们的中性类似物（11）和（12）更有效。
Cationic iridium(I), rhodium(I) complexes containing bis(1-methylimidazol-2-yl) methane, bim, [M(bim)(CO)(2)]BPh4 (M=Ir (1), Rh (2)); bis(pyrazol-1-yl) methane, bpm, [M(bpm)(CO)(2)]BPh4 (M=Ir (3), Rh (4)) have been shown to be effective in catalysing the regioselective addition of thiophenol to a series of alkynes. Analogous cationic and neutral Ir(I), Rh(I) complexes with the novel mixed P,N-donor bidentate ligand 1-(2-diphenylphosphino) ethylpyrazole, PyP (5), [M(PyP)(COD)]BPh4 ( M=Ir (6), Rh (7), COD=1,5-cyclooctadiene); [Rh(PyP)(COD)]BF4 (8); [Ir(PyP)(CO)(2)]BPh4 (9); [Rh(PyP)(CO)(2)]BF4 (10); [M(PyP)(CO)Cl] (M=Ir (11), Rh (12)) have also been synthesised, and characterised by NMR. The solid-state structures of (6), (7), (11) and (12) have been determined by single-crystal X-ray diffraction analysis. The metal complexes (9)-(12) with the mixed P,N-donor ligand, PyP are in most cases more effective in promoting the hydrothiolation of alkynes in comparison with the analogous complexes (1) -(4) with N,N-donor ligands. The iridium complexes were significantly more effective than their rhodium analogues in promoting the hydrothioloation of alkynes. The cationic complexes (9) and (10) are more effective as catalysts for the hydrothiolation of alkynes than their neutral analogues (11) and (12).