Rhodium(I) and iridium(I) complexes containing bidentate phosphine-imidazolyl donor ligands as catalysts for the hydroamination and hydrothiolation of alkynes
Rhodium(I) and iridium(I) complexes containing bidentate phosphine-imidazolyl donor ligands as catalysts for the hydroamination and hydrothiolation of alkynes
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DOI：
10.1039/b821188d
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发表时间：
2009-05-14
影响因子：
4
通讯作者：
Turner, Peter
中科院分区：
文献类型：
--
作者：
Field, Leslie D.;Messerle, Barbara A.;Turner, Peter
一系列新颖的阳离子和中性铑和铱络合物，其含有通式[M（ImP）（COD）] BPh 4的双齿膦-咪唑基供体配体，（M = Rh，ImP ImP2，3; ImP1a，4a; ImP1b，4b和M = Ir，ImP = ImP2，5; ImP1a，6a和ImP1b，6b），[Ir（Imp）（CO）（2）]BPh4（ImP = ImP2，7; ImP1a，8a和ImP1b，8b）、[Rh（ImP1b）（CO）（2）]BPh4（10b）和[M（ImP）（CO）Cl]（M = Rh，Imp = ImP 2，11; ImP 1b，12和M = Ir，ImP = ImP 2，13; ImP 1b，14）其中COD = 1，5-环辛烷，ImP 2 = 1-甲基-2-[成功地合成了2-（二苯基膦基）乙基]咪唑，1; ImP 1a = 1-甲基-2-[（二苯基膦基）甲基]咪唑，2a和ImP 1b = 2-[（二异丙基膦基）甲基] 1-甲基咪唑，2b。用单晶X射线衍射分析测定了化合物3、6 a、11和12的固态结构。这些配合物中的许多作为4-戊炔-1-胺到2-甲基-1-吡咯啉的分子内氢胺化的催化剂是有效的。阳离子络合物比类似的中性络合物明显更有效。阳离子铱配合物8b，含有膦-咪唑基配体与磷供体上的庞大的异丙基，是更有效的比类似的配合物与苯基取代基油的磷供体原子，7和8a。配合物7-8b在催化苯硫酚加成到一系列末端炔上也是中等有效的。与氢胺化反应相反，在磷供体上放置异丙基导致所得金属络合物作为氢硫醇化反应催化剂的反应性降低。
A series of novel cationic and neutral rhodium and iridium complexes containing bidentate phosphine-imidazolyl donor ligands of the general formulae [M(ImP)(COD)]BPh4 (M = Rh, ImP ImP2,3; ImP1a, 4a; ImP1b, 4b and M = Ir, ImP = ImP2,5; ImP1a, 6a and ImP1b, 6b), [Ir(Imp)(CO)(2)]BPh4 (ImP = ImP2,7; ImP1a, 8a and ImP1b, 8b), [Rh(ImP1b)(CO)(2)]BPh4 (10b) and [M(ImP)(CO)Cl] (M = Rh, Imp = ImP2, 11; ImP1b, 12 and M = Ir, ImP = ImP2, 13; ImP1b, 14) where COD = 1,5-cyclooctadiene, ImP2 = 1-methyl-2-[(2-(diphenylphosphino)ethyl]imidazole, 1; ImP1a = 1-methyl-2-[(diphenylphosphino)methyl]imidazole, 2a and ImP1b = 2-[(diisopropylphosphino)methyl]I -methylimidazole, 2b were successfully synthesised. The solid state structures of 3, 6a, I I and 12 were determined by single crystal X-ray diffraction analysis. A number of these complexes are effective as catalysts for the intramolecular hydroamination of 4-pentyn-1-amine to 2-methyl-1-pyrroline. The cationic complexes are significantly more effective than analogous neutral complexes. The cationic iridium complex 8b, containing the phosphine-imidazolyl ligand with the bulky isopropyl groups on the phosphorus donor, is more efficient than analogous complexes with the phenyl substituents oil the phosphorus donor atom, 7 and 8a. The complexes 7-8b are also moderately effective in catalysing the addition of thiophenol to a range of terminal alkynes. In contrast to the hydroamination reaction, placement of the isopropyl group Oil the phosphorus donor leads to a decrease in the reactivity of the resulting Metal complexes as catalysts for the hydrothiolation reaction.