trans-dichlorobis(N,N'-dicyclohexylglyoxal diimine)ruthenium(II) | 164298-76-4

• 英文名称: trans-dichlorobis(N,N'-dicyclohexylglyoxal diimine)ruthenium(II)
• CAS: 164298-76-4；164454-84-6
• 化学式: C₂₈H₄₈Cl₂N₄Ru
• 分子量: 612.692
• InChiKey: UDZYOSOQLVFFFS-APRIUZBBSA-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：

  trans-dichlorobis(N,N'-dicyclohexylglyoxal diimine)ruthenium(II) 在 (NH₄)4Ce(SO₄)4*2H₂O 、 water 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 生成 trans-dichloro(N-cyclohexyl(cyclohexylimino)acetamidato)(N,N'-dicyclohexylglyoxal diimine)ruthenium(III)
  参考文献：
  名称：

  Amide Formation from Aldimine and Water Promoted by Coordinated Metal Redox. Chemistry of a Family of Isomeric RuII(diimine)2Cl2, RuIII(diimine)2Cl2+, and RuIII(diimine)(amide-imine)Cl2 Complexes

  摘要：

  The relevant N,N-coordinating ligands are RN=(H)-C(H)=NR (general abbreviation D, specific abbreviations D-1 and D-2 for R = cyclohexyl and p-tolyl, respectively) and [RN=C(H)-C(=O)-NR](-) (abbreviations A, A(1), A(2). Oxidation of cis- and trans-(RuD2Cl2)-D-II by aqueous cerium(IV) (H2O2 can also be used for trans-RuD2Cl2) affords in excellent yield the amide complexes cis- and trans-Ru(III)DACl(2) with retention of parental isomeric structure. Spectral and magnetic characterization data of the complexes are reported along with the X-ray structures of cis-RuD12Cl2 . PhMe and cis-RuD(1)A(1)Cl(2) . CH2Cl2. The ruthenium(III)-ruthenium(II) couples of the complexes follow E(1/2) systematics (other things remaining the same in each case): geometry, cis > trans; ligand, D > A; substituent, p-tolyl > cyclohexyl. The (RuD2Cl2+)-D-III moiety has been electrogenerated in solution, and cis- [(RuD2Cl2)-D-III-Cl-1]ClO4 has been isolated and characterized in the pure state. The conversion RuD2Cl2 --> RuDACl(2) actually occurs via RuD2Cl2+, which reacts with water, affording the amide complex. The reaction is first order with respect to both RuD2Cl2+ and H2O, and the activation parameters are Delta h(double dagger) = 12.5 kcal mol(-1) and Delta S-double dagger = -29.8 eu in the case of trans-(RuD2Cl2)-Cl-2. It is proposed that the water molecule adds to the azomethine function and the a-hydroxy amine function of the adduct is rapidly oxidized via an induced electron transfer pathway. The net reactions are as follows: RuD2Cl2 --> RuD2Cl2+ + e; RuD2Cl2+ + H2O --> RuDACl(2) + 2e + 3H(+). A crucial reaction condition appears to be the easy accessibility of two oxidation states of the metal ion related by facile transfer of one electron, the higher oxidation state being sufficiently polarizing to induce water binding at the aldimine site. Crystal data for the complexes are as follows: cis-(RuD2Cl2)-Cl-1 . PhME, crystal system monoclinic, space group P2(1)/c, a = 14.808(6) Angstrom, b = 19.442(7) Angstrom, c = 13.989(6) Angstrom, beta = 117.18(3)degrees, V = 3583(2) A(3), Z = 4, R = 3.70%, R(w) = 4.31%; cis-RuD(1)A(1)Cl(2) . CH2Cl2, crystal system monoclinic, space group P2(1)/c, a = 11.295(4) Angstrom, b = 27.064(14) Angstrom, c = 12.064(4) Angstrom, beta = 107.52(2)degrees, V = 3517(2) A(3), Z = 4, R = 6.53%, R(w) = 6.95%.

  DOI：

  10.1021/ic00116a025
• 作为产物：
  描述：

  dichlorotetrakis(dimethylsulfoxide)ruthenium(II) 、 N,N'-di-cyclohexyl-1,4-diazabuta-1,3-diene 以 乙醇 为溶剂， 以75%的产率得到trans-dichlorobis(N,N'-dicyclohexylglyoxal diimine)ruthenium(II)
  参考文献：
  名称：

  Amide Formation from Aldimine and Water Promoted by Coordinated Metal Redox. Chemistry of a Family of Isomeric RuII(diimine)2Cl2, RuIII(diimine)2Cl2+, and RuIII(diimine)(amide-imine)Cl2 Complexes

  摘要：

  The relevant N,N-coordinating ligands are RN=(H)-C(H)=NR (general abbreviation D, specific abbreviations D-1 and D-2 for R = cyclohexyl and p-tolyl, respectively) and [RN=C(H)-C(=O)-NR](-) (abbreviations A, A(1), A(2). Oxidation of cis- and trans-(RuD2Cl2)-D-II by aqueous cerium(IV) (H2O2 can also be used for trans-RuD2Cl2) affords in excellent yield the amide complexes cis- and trans-Ru(III)DACl(2) with retention of parental isomeric structure. Spectral and magnetic characterization data of the complexes are reported along with the X-ray structures of cis-RuD12Cl2 . PhMe and cis-RuD(1)A(1)Cl(2) . CH2Cl2. The ruthenium(III)-ruthenium(II) couples of the complexes follow E(1/2) systematics (other things remaining the same in each case): geometry, cis > trans; ligand, D > A; substituent, p-tolyl > cyclohexyl. The (RuD2Cl2+)-D-III moiety has been electrogenerated in solution, and cis- [(RuD2Cl2)-D-III-Cl-1]ClO4 has been isolated and characterized in the pure state. The conversion RuD2Cl2 --> RuDACl(2) actually occurs via RuD2Cl2+, which reacts with water, affording the amide complex. The reaction is first order with respect to both RuD2Cl2+ and H2O, and the activation parameters are Delta h(double dagger) = 12.5 kcal mol(-1) and Delta S-double dagger = -29.8 eu in the case of trans-(RuD2Cl2)-Cl-2. It is proposed that the water molecule adds to the azomethine function and the a-hydroxy amine function of the adduct is rapidly oxidized via an induced electron transfer pathway. The net reactions are as follows: RuD2Cl2 --> RuD2Cl2+ + e; RuD2Cl2+ + H2O --> RuDACl(2) + 2e + 3H(+). A crucial reaction condition appears to be the easy accessibility of two oxidation states of the metal ion related by facile transfer of one electron, the higher oxidation state being sufficiently polarizing to induce water binding at the aldimine site. Crystal data for the complexes are as follows: cis-(RuD2Cl2)-Cl-1 . PhME, crystal system monoclinic, space group P2(1)/c, a = 14.808(6) Angstrom, b = 19.442(7) Angstrom, c = 13.989(6) Angstrom, beta = 117.18(3)degrees, V = 3583(2) A(3), Z = 4, R = 3.70%, R(w) = 4.31%; cis-RuD(1)A(1)Cl(2) . CH2Cl2, crystal system monoclinic, space group P2(1)/c, a = 11.295(4) Angstrom, b = 27.064(14) Angstrom, c = 12.064(4) Angstrom, beta = 107.52(2)degrees, V = 3517(2) A(3), Z = 4, R = 6.53%, R(w) = 6.95%.

  DOI：

  10.1021/ic00116a025