[H2NEt2][((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)ClRu(μ-Cl)3RuCl((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)]

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [H2NEt2][((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)ClRu(μ-Cl)3RuCl((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)]
• 英文别名: Dichlororuthenium;diethylazanium;[1-(2-diphenylphosphanylnaphthalen-1-yl)naphthalen-2-yl]-diphenylphosphane;chloride
• 化学式: C₄H₁₂N*C₈₈H₆₄Cl₅P₄Ru₂
• 分子量: 1698.92
• InChiKey: WREPVNXWMUUSKZ-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  21.38
• 重原子数：
  104
• 可旋转键数：
  16
• 环数：
  16.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  16.6
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  RuCl2((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)(PPh3) 、 二乙胺盐酸盐 以 二氯甲烷 为溶剂， 以63%的产率得到[H2NEt2][((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)ClRu(μ-Cl)3RuCl((R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl)]
  参考文献：
  名称：

  Triply-bridged diruthenium(II) 1,4-bis(diphenylphosphino)butane (dppb) and (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) complexes, including structural characterisation of [(dppb) ClRu(μ-D2O)-(μ-Cl)2RuCl(dppb)], [(η2-H2) (dppb)Ru(μ-Cl)3RuCl(dppb)] and the [(dppb)ClRu(μ-Cl)3RuCl(dppb)]− anion

  摘要：

  Several triply-bridged diruthenium(II)(1,4-bis(diphenylphosphino)butane) complexes were synthesised and characterised by elemental analysis, UV-Vis, NMR and IR spectroscopies, The solid-state structures of [(dppb)ClRu(mu-D2O)(mu-Cl)(2)RuCl(dppb)] (1), [(eta(2)-H-2) (dppb)Ru(mu-Cl)(3)RuCl(dppb)] (2) and [TMP][(dppb)ClRu(mu-Cl)(3)RuCl(dppb)] (3) were established by X-ray crystallographic analyses (TMP=1,1,3-trimethyl-2,3-dihydroperimidinium; dppb = Ph2P(CH2)(4)PPh2). Crystals of 1.1.5C(6)D(6), 2.1.5C(7)D(8) and 3.2Me(2)CO.2H(2)O are all monoclinic, space groups P2(1)/c, P2(1)/n and C2/c, respectively, with Z=4: a=16.8681(6), b=13.3542(4), c=26.4966(7) Angstrom, beta=91.877(1)degrees for 1.1.5C(6)D(6); a = 19.8123(1), b=14.5246(2), c = 22.1803(1) Angstrom, beta=106.58(1)degrees for 2.1.5C(7)D(8); a=21.596(2), b=16.019(2), c=22.317(2) Angstrom, beta=106.15(1)degrees for 3.2Me(2)CO . 2H(2)O. The structures of 1 and 2 were salved by direct methods while 3 was solved by heavy atom methods and all were refined by full-matrix least-squares procedures to R-1 = 0.0433, 0.0612 and R = 0.039 (wR(2) = 0.0709 (1), 0.1178 (2)) for 7751, 6757 and 5237 reflections with I greater than or equal to 2 sigma(I) for 1 and 2 and I greater than or equal to 3 sigma(I) for 3, respectively, Complex I was also studied in the solid-state by P-31 CP/MAS NMR spectroscopy. The bromo- and iodo-analogues of 1 were prepared, and these three species were screened as catalysts for hydrogenation of aldimines. The complexes [H2NR2][{RuCl(P-P)}(2)(mu-Cl)(3)] were synthesised by the addition of NR3 or [H2NR2]Cl to RuCl2(P-P)(PPh3), where P-P = dppb or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) and R =Et, n-Bu or n-Oct. The syntheses of [(DMA)(2)H][(PPh3)(2)ClRu(mu-Cl)(3)RuCl(PPh3)(2)], [(py)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] and [(C2H4)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] were also accomplished (DMA = N,N-dimethylacetamide; py = pyridine). (C) 1998 Elsevier Science S.A.

  DOI：

  10.1016/s0020-1693(97)05833-7

文献信息

• Convenient synthesis of anionic dinuclear ruthenium(II) complexes [NR2H2][{RuCl(diphosphine)}2(μ-Cl)3] [diphosphine=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, 2,2′-bis(di(p-tolyl)phosphino)-1,1′-binaphthyl, and 1,2-bis(diphenylphosphino)benzene]: crystal structure of [NEt2H2][{RuCl(1,2-bis(diphenylphosphino)benzene)}2(μ-Cl)3]
  作者：Kazushi Mashima、Tomoko Nakamura、Yutaka Matsuo、Kazuhide Tani

  DOI：10.1016/s0022-328x(00)00192-3

  日期：2000.8

  [NR2H2][RuCl(diphosphine)}2(μ-Cl)3]. A one-pot mixture of BINAP or its derivative, [RuCl2(η6-arene)]2, and NR2H2Cl produced salts of the anionic dinuclear complexes which can be applied as catalysts for the asymmetric hydrogenation of ketonic substrates such as acetol and methyl acetoacetate with high activity and high enantioselectivity. The anionic face-sharing bioctahedral structure of these complexes

  我们报告了实用的一锅法合成的具有螯合二膦配体，BINAP和DPB的阴离子双核钌配合物的二烷基铵盐，其化学式为[NEt 2 H 2 ] [RuCl（diphosphine）} 2（μ-Cl）3 ] [ 2a：二膦＝ 2，2′-双（二苯基膦基）-1，1′-联萘基；6a：2，2′-双（二（对甲苯基）膦基）-1，1′-联萘基；8a：1，2-双（二苯基膦基）苯]。阳离子钌络合物的治疗，将[RuCl（η 6 - p -cymene）（二膦）]氯（4）与稍过量的净2 ħ 2 Cl（上图5a）定量提供2a，6a和8a。与各种二烷基铵盐5b - f的类似反应得到相应的盐，[NR 2 H 2 ] [RuCl（二膦）} 2（μ-Cl）3 ]。BINAP或它的衍生物，将[RuCl的一锅混合物2（η 6 -arene）] 2，和NR 2 ħ 2Cl制得的阴离子双核络合物的盐可以用作催化剂，用于酮底物如丙酮醇和乙
• Triply-bridged diruthenium(II) 1,4-bis(diphenylphosphino)butane (dppb) and (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) complexes, including structural characterisation of [(dppb) ClRu(μ-D2O)-(μ-Cl)2RuCl(dppb)], [(η2-H2) (dppb)Ru(μ-Cl)3RuCl(dppb)] and the [(dppb)ClRu(μ-Cl)3RuCl(dppb)]− anion
  作者：Kenneth S. MacFarlane、Ian S. Thorburn、Paul W. Cyr、Daniel E.K.-Y. Chau、Steven J. Rettig、Brian R. James

  DOI：10.1016/s0020-1693(97)05833-7

  日期：1998.4

  Several triply-bridged diruthenium(II)(1,4-bis(diphenylphosphino)butane) complexes were synthesised and characterised by elemental analysis, UV-Vis, NMR and IR spectroscopies, The solid-state structures of [(dppb)ClRu(mu-D2O)(mu-Cl)(2)RuCl(dppb)] (1), [(eta(2)-H-2) (dppb)Ru(mu-Cl)(3)RuCl(dppb)] (2) and [TMP][(dppb)ClRu(mu-Cl)(3)RuCl(dppb)] (3) were established by X-ray crystallographic analyses (TMP=1,1,3-trimethyl-2,3-dihydroperimidinium; dppb = Ph2P(CH2)(4)PPh2). Crystals of 1.1.5C(6)D(6), 2.1.5C(7)D(8) and 3.2Me(2)CO.2H(2)O are all monoclinic, space groups P2(1)/c, P2(1)/n and C2/c, respectively, with Z=4: a=16.8681(6), b=13.3542(4), c=26.4966(7) Angstrom, beta=91.877(1)degrees for 1.1.5C(6)D(6); a = 19.8123(1), b=14.5246(2), c = 22.1803(1) Angstrom, beta=106.58(1)degrees for 2.1.5C(7)D(8); a=21.596(2), b=16.019(2), c=22.317(2) Angstrom, beta=106.15(1)degrees for 3.2Me(2)CO . 2H(2)O. The structures of 1 and 2 were salved by direct methods while 3 was solved by heavy atom methods and all were refined by full-matrix least-squares procedures to R-1 = 0.0433, 0.0612 and R = 0.039 (wR(2) = 0.0709 (1), 0.1178 (2)) for 7751, 6757 and 5237 reflections with I greater than or equal to 2 sigma(I) for 1 and 2 and I greater than or equal to 3 sigma(I) for 3, respectively, Complex I was also studied in the solid-state by P-31 CP/MAS NMR spectroscopy. The bromo- and iodo-analogues of 1 were prepared, and these three species were screened as catalysts for hydrogenation of aldimines. The complexes [H2NR2][RuCl(P-P)}(2)(mu-Cl)(3)] were synthesised by the addition of NR3 or [H2NR2]Cl to RuCl2(P-P)(PPh3), where P-P = dppb or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) and R =Et, n-Bu or n-Oct. The syntheses of [(DMA)(2)H][(PPh3)(2)ClRu(mu-Cl)(3)RuCl(PPh3)(2)], [(py)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] and [(C2H4)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] were also accomplished (DMA = N,N-dimethylacetamide; py = pyridine). (C) 1998 Elsevier Science S.A.