Synthesis and reactivity of ruthenium tridentate bis-phosphinite ligand complexes
作者:Michael J. Sgro、Douglas W. Stephan
DOI:10.1039/c3dt51065d
日期:——
The tridentate ligands E(CH2CH2OPiPr2)2 (E = NH 1, E = S 2) were employed in the synthesis of a number of ruthenium complexes. Reaction of these ligands with (Ph3P)3RuCl2 afforded the dimers [Ru(HN(CH2CH2OPiPr2)2)Cl(μ-Cl)]2 (3) and [(Ru(E(CH2CH2OPiPr2)2))2(μ-Cl)3][X] (E = NH, X = PF64, E = S, X = Cl 5), respectively. Using (Ph3P)3RuHCl in reactions with 1 gave Ru(NH(CH2CH2OPiPr2)2)(PPh3)HCl (6) while addition of pyridine and 2, gave Ru(S(CH2CH2OPiPr2)2)(py)HCl (7). Treatment of 6 or 7 with NaBPh4 resulted in the formation of the η6-arene complexes RuH(E(CH2CH2OPiPr2)2)2(η6-C6H5BPh3) (E = NH 8, E = S 9) while reactions with K[B(C6F5)4] gave the salts [RuH(E(CH2CH2OPiPr2)2)(L)][B(C6F5)4] (E = NH, L = PPh310, E = S, L = py 12). Compounds 6 and 7 react with CO giving RuH(HN(CH2CH2OPiPr2)2)(CO)Cl (15) and [RuH(S(CH2CH2OPiPr2)2(py)(CO)]Cl (16) respectively, while reaction of 6, 10 or 12 with dihydrogen gave RuH(HN(CH2CH2OPiPr2)2)(H2)Cl (18) and RuH(E(CH2CH2OPiPr2)2)(L)(H2)][B(C6F5)4] (E = NH, L = PPh319, E = S, L = py 20). The complexes 4–12, 15 and 16 are shown to catalyze the dehydrogenation of HMe2NBH3.
三叉配体 E(CH2CH2OPiPr2)2(E = NH 1,E = S 2)被用于合成多种钌配合物。这些配体与 (Ph3P)3RuCl2 反应分别得到了二聚体 [Ru(HN(CH2CH2OPiPr2)2)Cl(μ-Cl)]2 (3) 和 [(Ru(E(CH2CH2OPiPr2)2))2(μ-Cl)3][X](E = NH,X = PF64,E = S,X = Cl 5)。使用 (Ph3P)3RuHCl 与 1 反应得到 Ru(NH(CH2CH2OPiPr2)2)(PPh3)HCl (6),而加入吡啶和 2 则得到 Ru(S(CH2CH2OPiPr2)2)(py)HCl (7)。用 NaBPh4 处理 6 或 7 会生成 η6-arene 复合物 RuH(E(CH2CH2OPiPr2)2)2(η6-C6H5BPh3) (E = NH 8、E = S 9),而与 K[B(C6F5)4] 反应则生成盐类 [RuH(E(CH2CH2OPiPr2)2)(L)][B(C6F5)4](E = NH,L = PPh310,E = S,L = py 12)。化合物 6 和 7 与 CO 反应,分别得到 RuH(HN(CH2CH2OPiPr2)2)(CO)Cl (15) 和 [RuH(S(CH2CH2OPiPr2)2(py)(CO)]Cl (16),而化合物 6、10 或 12 与二氢反应,则得到 RuH(HN(CH2CH2OPiPr2)2)(CO)Cl (16)、10或12与二氢反应则得到 RuH(HN(CH2CH2OPiPr2)2)(H2)Cl (18) 和 RuH(E(CH2CH2OPiPr2)2)(L)(H2)][B(C6F5)4] (E = NH,L = PPh319,E = S,L = py 20)。复合物 4-12、15 和 16 可以催化 HMe2NBH3 的脱氢反应。