(η(6)-p-cymene)Ru(Cl)(μ-C3H3N2C3H2N2)RhCl(CO)2 | 161015-48-1

• 英文名称: (η(6)-p-cymene)Ru(Cl)(μ-C3H3N2C3H2N2)RhCl(CO)2
• CAS: 161015-48-1
• 化学式: C₁₈H₁₉Cl₂N₄O₂RhRu
• 分子量: 598.256
• InChiKey: BHTIVXLVTGUUOV-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η(6)-p-cymene)Ru(Cl)(μ-C3H3N2C3H2N2)RhCl(CO)2 在 KOH 作用下， 以 甲醇 为溶剂， 以82%的产率得到[(η(6)-p-cymene)RuCl(μ-(C3H2N2)2)Rh(CO)2]2
  参考文献：
  名称：

  Heterobi- and Heterotetranuclear RuRh and RuIr Complexes with 2,2'-Biimidazolate and 2,2'-Bibenzimidazolate Anions as Bridging Ligands

  摘要：

  The reaction of the dimer {(eta(6)-p-cymene)RuCl}(2)(mu-Cl)(2) (p-cymene = p-isopropylmethylbenzene) with 2,2'-biimidazole (H(2)Bim) afforded the chloride complex (eta(6)-p-cymene)Ru(H(2)Bim)Cl Cl (1) which has also been isolated as the tetrafluoroborate salt (eta(6)-p-cymene)Ru(H(2)Bim)Cl BF4 (2) by metathesis with NaBF4. Complex 1 underwent reaction with M(acac)L(2) yielding the corresponding heterobinuclear species (eta(6)-p-cymene)ClRu(mu-HBim)MClL(2) (M = Rh; L(2) = cis,cis-1,5-cyclooctadiene (COD) (3), (CO)(2) (4); M = Ir, L(2) = COD (5) . Complexes 3-5 exhibit a dynamic behavior which equilibrates the two imidazole rings of the HBim bridging ligand. The reaction of 4 with KOH led to two tetranuclear isomers (eta(6)-p-cymene)ClRu(mu-Bim)Rh(CO)(2) (2) (6) which in solution reached an equilibrium with a K value for the process 6b reversible arrow 6a less than or equal to 0.11. Reaction of (eta(6)-p-cymene)Ru(acac)Cl with Rh(HBim)(COD) afforded the heterobinuclear complex (eta(6)-p-cymene)Ru(acac)(mu-HBim)Rh(COD) A (A = Cl (7), BF4 (8)). At room temperature the Rh(HBim)(COD) moiety of complexes 7 and 8 rotates rapidly around the Ru-N bond, but this process stops at 223 K. (eta(6)-p-cymene)Ru(acac)Cl and (eta(6)-p-cymene)Ru(acac)(PPh(3)) BF4 reacted with 2,2'-bibenzimidazole (H-2-Bbzim) rendering (eta(6)-p-cymene)Ru(HBbzim)Cl (9) and (eta(6)-p-cymene)Ru(HBbzim)(PPh(3)) BF4 (10), respectively. Complex 9 undergoes reaction with M(acac)L(2) yielding (eta(6)-p-cymene)ClRu(mu-Bbzim)ML(2) (n) (M = Rh; L(2) = COD (n = 1) (11), norborna-2,5-diene (NBD) (n = 2) (12), (CO)(2) (n = 2) (13). M = Ir; L(2) = COD (n = 1) (14)). The molecular structure of complex 12 has been determined. Crystals are triclinic, space group P $($) over bar$$ 1, with cell parameters a = 12.998(1) Angstrom, b = 14.035(1) Angstrom, c = 18.081(2) Angstrom, alpha = 79.864(4)degrees, beta = 78.046(5)degrees, gamma = 73.326(7)degrees, and Z = 2. The compound is tetranuclear with two Bbzim(2-) ligands bridging the metal atoms. Each Bbzim(2-) coordinates to the metals in an unsymmetrical tetradentate manner through its four nitrogen atoms, chelated to the Ru atoms and bonded in an unidentate manner to the two Rh atoms. The cationic complex 10 undergo reaction with the acetylacetonates M(acac)L(2) yielding the cationic binuclear complexes (eta(6)-p-cymene)(PPh(3))Ru(mu-Bbzim)ML(2) BF4 (M = Rh; L(2) = COD (15), NBD (16), (CO)(2) (17). M = Ir; L(2) = COD (18)). Carbonylation of 18 afforded (eta(6)-p-cymene)(PPh(3))Ru(mu-Bbzim)Ir(CO)(2) BF4 (19) and complex 17 could analogously be obtained from complexes 15 or 16. The molecular structure of complex 19 has been determined by diffractometric methods. Crystals are monoclinic, space group P2(1)/c, with cell parameters a = 11.586(2) Angstrom, b = 20.489(2) Angstrom, c = 17.226(1) Angstrom, beta = 95.34(1)degrees, and Z = 4. In the solid state, two complex cations (eta(6)-p-cymene)(PPh(3))Ru(mu-Bbzim)Ir(CO)(2) related by an inversion center are joined by an intermetallic Ir-Ir interaction (3.0808(5) Angstrom).The cation consists of a Ru and an Ir atom connected by a Bbzim(2-) anion that chelates both metals through four nitrogen atoms. Complexes 11, 14, and 15-19 are active catalysts for the homogeneous hydrogenation of cyclohexene. Kinetic studies showed that the reduction catalyzed by 14 is first-order in catalyst concentration and second-order in hydrogen concentration.

  DOI：

  10.1021/om00004a069
• 作为产物：
  描述：

  (η(6)-p-cymene)Ru(Cl)(μ-C3H3N2C3H2N2)RhCl(1,5-cyclooctadiene) 、 一氧化碳 以 二氯甲烷 为溶剂， 以60%的产率得到(η(6)-p-cymene)Ru(Cl)(μ-C3H3N2C3H2N2)RhCl(CO)2
  参考文献：
  名称：

  Heterobi- and Heterotetranuclear RuRh and RuIr Complexes with 2,2'-Biimidazolate and 2,2'-Bibenzimidazolate Anions as Bridging Ligands

  摘要：

  The reaction of the dimer {(eta(6)-p-cymene)RuCl}(2)(mu-Cl)(2) (p-cymene = p-isopropylmethylbenzene) with 2,2'-biimidazole (H(2)Bim) afforded the chloride complex (eta(6)-p-cymene)Ru(H(2)Bim)Cl Cl (1) which has also been isolated as the tetrafluoroborate salt (eta(6)-p-cymene)Ru(H(2)Bim)Cl BF4 (2) by metathesis with NaBF4. Complex 1 underwent reaction with M(acac)L(2) yielding the corresponding heterobinuclear species (eta(6)-p-cymene)ClRu(mu-HBim)MClL(2) (M = Rh; L(2) = cis,cis-1,5-cyclooctadiene (COD) (3), (CO)(2) (4); M = Ir, L(2) = COD (5) . Complexes 3-5 exhibit a dynamic behavior which equilibrates the two imidazole rings of the HBim bridging ligand. The reaction of 4 with KOH led to two tetranuclear isomers (eta(6)-p-cymene)ClRu(mu-Bim)Rh(CO)(2) (2) (6) which in solution reached an equilibrium with a K value for the process 6b reversible arrow 6a less than or equal to 0.11. Reaction of (eta(6)-p-cymene)Ru(acac)Cl with Rh(HBim)(COD) afforded the heterobinuclear complex (eta(6)-p-cymene)Ru(acac)(mu-HBim)Rh(COD) A (A = Cl (7), BF4 (8)). At room temperature the Rh(HBim)(COD) moiety of complexes 7 and 8 rotates rapidly around the Ru-N bond, but this process stops at 223 K. (eta(6)-p-cymene)Ru(acac)Cl and (eta(6)-p-cymene)Ru(acac)(PPh(3)) BF4 reacted with 2,2'-bibenzimidazole (H-2-Bbzim) rendering (eta(6)-p-cymene)Ru(HBbzim)Cl (9) and (eta(6)-p-cymene)Ru(HBbzim)(PPh(3)) BF4 (10), respectively. Complex 9 undergoes reaction with M(acac)L(2) yielding (eta(6)-p-cymene)ClRu(mu-Bbzim)ML(2) (n) (M = Rh; L(2) = COD (n = 1) (11), norborna-2,5-diene (NBD) (n = 2) (12), (CO)(2) (n = 2) (13). M = Ir; L(2) = COD (n = 1) (14)). The molecular structure of complex 12 has been determined. Crystals are triclinic, space group P $($) over bar$$ 1, with cell parameters a = 12.998(1) Angstrom, b = 14.035(1) Angstrom, c = 18.081(2) Angstrom, alpha = 79.864(4)degrees, beta = 78.046(5)degrees, gamma = 73.326(7)degrees, and Z = 2. The compound is tetranuclear with two Bbzim(2-) ligands bridging the metal atoms. Each Bbzim(2-) coordinates to the metals in an unsymmetrical tetradentate manner through its four nitrogen atoms, chelated to the Ru atoms and bonded in an unidentate manner to the two Rh atoms. The cationic complex 10 undergo reaction with the acetylacetonates M(acac)L(2) yielding the cationic binuclear complexes (eta(6)-p-cymene)(PPh(3))Ru(mu-Bbzim)ML(2) BF4 (M = Rh; L(2) = COD (15), NBD (16), (CO)(2) (17). M = Ir; L(2) = COD (18)). Carbonylation of 18 afforded (eta(6)-p-cymene)(PPh(3))Ru(mu-Bbzim)Ir(CO)(2) BF4 (19) and complex 17 could analogously be obtained from complexes 15 or 16. The molecular structure of complex 19 has been determined by diffractometric methods. Crystals are monoclinic, space group P2(1)/c, with cell parameters a = 11.586(2) Angstrom, b = 20.489(2) Angstrom, c = 17.226(1) Angstrom, beta = 95.34(1)degrees, and Z = 4. In the solid state, two complex cations (eta(6)-p-cymene)(PPh(3))Ru(mu-Bbzim)Ir(CO)(2) related by an inversion center are joined by an intermetallic Ir-Ir interaction (3.0808(5) Angstrom).The cation consists of a Ru and an Ir atom connected by a Bbzim(2-) anion that chelates both metals through four nitrogen atoms. Complexes 11, 14, and 15-19 are active catalysts for the homogeneous hydrogenation of cyclohexene. Kinetic studies showed that the reduction catalyzed by 14 is first-order in catalyst concentration and second-order in hydrogen concentration.

  DOI：

  10.1021/om00004a069