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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and reactivity of ruthenium tridentate bis-phosphinite ligand complexes
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Synthesis and reactivity of ruthenium tridentate bis-phosphinite ligand complexes

机译:三齿钌双亚膦酸酯配体配合物的合成与反应性

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The tridentate ligands E(CH_2CH_2OPiPr _2)_2 (E = NH 1, E = S 2) were employed in the synthesis of a number of ruthenium complexes. Reaction of these ligands with (Ph _3P)_3RuCl_2 afforded the dimers [Ru(HN(CH _2CH_2OPiPr_2)_2)Cl(μ-Cl)] _2 (3) and [(Ru(E(CH_2CH_2OPiPr_2) _2))_2(μ-Cl)_3][X] (E = NH, X = PF _64, E = S, X = Cl 5), respectively. Using (Ph_3P) _3RuHCl in reactions with 1 gave Ru(NH(CH_2CH _2OPiPr_2)_2)(PPh_3)HCl (6) while addition of pyridine and 2, gave Ru(S(CH_2CH_2OPiPr _2)_2)(py)HCl (7). Treatment of 6 or 7 with NaBPh _4 resulted in the formation of the η~6-arene complexes RuH(E(CH_2CH_2OPiPr_2)_2) _2(η~6-C_6H_5BPh_3) (E = NH 8, E = S 9) while reactions with K[B(C_6F_5)_4] gave the salts [RuH(E(CH_2CH_2OPiPr_2) _2)(L)][B(C_6F_5)_4] (E = NH, L = PPh_310, E = S, L = py 12). Compounds 6 and 7 react with CO giving RuH(HN(CH_2CH_2OPiPr_2)_2)(CO)Cl (15) and [RuH(S(CH_2CH_2OPiPr_2)_2(py)(CO)]Cl (16) respectively, while reaction of 6, 10 or 12 with dihydrogen gave RuH(HN(CH_2CH_2OPiPr_2)_2)(H _2)Cl (18) and RuH(E(CH_2CH_2OPiPr _2)_2)(L)(H_2)][B(C_6F_5) _4] (E = NH, L = PPh_319, E = S, L = py 20). The complexes 4-12, 15 and 16 are shown to catalyze the dehydrogenation of HMe _2NBH_3.
机译:三齿配体E(CH_2CH_2OPiPr _2)_2(E = NH 1,E = S 2)用于合成许多钌配合物。这些配体与(Ph _3P)_3RuCl_2反应得到二聚体[Ru(HN(CH _2CH_2OPiPr_2)_2)Cl(μ-Cl)] _2(3)和[(Ru(E(CH_2CH_2OPiPr_2)_2))_ 2(μ- Cl)_3] [X](E = NH,X = PF _64,E = S,X = Cl 5)。在与1的反应中使用(Ph_3P)_3RuHCl得到Ru(NH(CH_2CH _2OPiPr_2)_2)(PPh_3)HCl(6)并添加吡啶和2得到Ru(S(CH_2CH_2OPiPr _2)_2)(py)HCl(7) 。用NaBPh _4处理6或7导致形成η〜6-芳烃配合物RuH(E(CH_2CH_2OPiPr_2)_2)_2(η〜6-C_6H_5BPh_3)(E = NH 8,E = S 9),同时与K [B(C_6F_5)_4]得到盐[RuH(E(CH_2CH_2OPiPr_2)_2)(L)] [B(C_6F_5)_4](E = NH,L = PPh_310,E = S,L = py 12)。化合物6和7与一氧化碳反应,分别得到RuH(HN(CH_2CH_2OPiPr_2)_2)(CO)Cl(15)和[RuH(S(CH_2CH_2OPiPr_2)_2(py)(CO)] Cl(16),用二氢10或12得到RuH(HN(CH_2CH_2OPiPr_2)_2)(H _2)Cl(18)和RuH(E(CH_2CH_2OPiPr _2)_2)(L)(H_2)] [B(C_6F_5)_4](E = NH ,L = PPh_319,E = S,L = py 20),显示配合物4-12、15和16催化HMe _2NBH_3的脱氢。

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