[MeSi(SiMe2N(4-CH3C6H4))3]Zr-Ru(CO)2(Cp) | 175915-53-4

• 英文名称: [MeSi(SiMe2N(4-CH3C6H4))3]Zr-Ru(CO)2(Cp)
• 英文别名: [Me2Si(SiMe2N(p-tolyl))3Zr-Ru(CO)2Cp]
• CAS: 175915-53-4
• 化学式: C₃₅H₄₇N₃O₂RuSi₄Zr
• 分子量: 846.413
• InChiKey: ZSBVDMWUAPURTP-UHFFFAOYSA-N

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：

  四甲基亚砜 、 [MeSi(SiMe2N(4-CH3C6H4))3]Zr-Ru(CO)2(Cp) 以 甲苯 为溶剂， 以28%的产率得到[Me2Si(SiMe2N(p-tolyl))3Zr(μ-O2C)Ru(CO)(S(CH2)4)Cp]
  参考文献：
  名称：

  Synthesis and Reactivity of Early−Late Heterodinuclear Complexes Stabilized by a Trisilylsilane-Based Tripodal Amido Ligand

  摘要：

  The reaction of the complexes [MeSi{SiMe2N(R)}(3)MX] (R = p-tolyl, 2-FC6H4; M = Ti, Zr, Hf; X = Cl, Br) with K[CpM'(CO)(2)] afforded the metal-metal bonded heterodinuclear complexes [MeSi{SiMe2N(R)}(3)M-M'(CO)(2)Cp] (M = Ti, Zr, Hf; M' = Fe, Ru; R = p-tolyl, 2-C6H4), all of which are thermally stable in the solid state and in solution. X-ray crystal structure analyses of the complexes [MeSi{SiMe2N(p-tol)}(3)M-M'(CO)(2)Cp] (M. M': Ti, Fe (3); Ti, Ru (4); Zr, Fe (5)) and [MeSi{SiMe2N(2-FC6H4)}(3)Ti-Fe(CO)(2)Cp] (9) established the presence of unsupported metal-metal bonds [3, Ti-Fe 2.360(1); 4, Ti-Ru 2.5609(8); 5, Zr-Fe 2,605(2); 9, Ti-Fe 2.433(4) Angstrom]. Reaction of the dinuclear complexes with isonitriles led to insertion of the substrate into the polar metal-metal bond and the formation of the metallaiminoacyl complexes [MeSi{SiMe2N(R)}(3)M{eta(2)-(C=NR')M'(CO)(2)Cp}] (M = Ti, Zr, Hf; M' = Fe, Ru; R p-tolyl, 2-C6H4; R' = Me, p-tolyl). The C-13 NMR resonances of the isonitrile-derived carbon nuclei linking the two metal centers are observed at remarkably low field (delta 267.8-303.8). The structural proposal for the insertion products was confirmed by an X-ray crystallographic study of [MeSi{SiMe2N(p-tol)}(3)Ti{eta(2)-(C=NMe)Ru(CO)(2)Cp]. When the heterobimetallic complex [Me2SO, Me(Ph)SO, (PhCH2)(2)SO, (CH2)(4)SO], was reacted with sulfoxides [Me2SO, Me(Ph)SO, (PhCH2)(2)SO, (CH2)(4)SO], immediate oxygen transfer to a carbonyl ligand occurred, generating the dinuclear complexes [MeSi(SiMe2-NTol)(3)Zr(mu-O2C)RuCp(CO){S(R)R'}] (R R' = Me (23a); R = Me, R' Ph (23b); R, R' = (CH2)(4) (23c); R, R' = PhCH2 (23d)), in which the two metal centers are linked by a CO2 ligand derived from a carbonyl ligand in the starting material. In the presence of a second equivalent of sulfoxide, the Lewis acid-base adducts [MeSi(SiMe(2)NTol)(3)Zr{OS(R)R'-kappa O}(mu-O2C)RuCp(CO){S(R)R'}] (R = R' = Me (24a); R = Me, R' = Ph (24b); R, R' = (CH2)(4) (24c)) were formed. An X-ray crystal structure analysis of 24a established the conversion of the carbonyl ligand to the bridging matallacarboxylate unit and the coordination of the thioether, formed in the oxygen transfer, to the Ru atom. The oxygen transfer from the sulfoxide to a carbonyl ligand was confirmed by an NMR study of the reaction using C-13-labeled carbonyl derivatives and O-17-labeled Me(Ph)SO.

  DOI：

  10.1021/ic990562n
• 作为产物：
  描述：

  K{Ru(η5-C5H5)(CO)2} 、 [MeSi(SiMe2N(p-tolyl))3ZrCl] 以 not given 为溶剂， 生成 [MeSi(SiMe2N(4-CH3C6H4))3]Zr-Ru(CO)2(Cp)
  参考文献：
  名称：

  A ‘passe-partout’ for the stabilization of highly polar unsupported M–M′ bonds (M = Ti, Zr, Hf; M′= Fe, Ru) and α-addition of the metal nucleophile–electrophile pairs to an isocyanide

  摘要：

  The coordination of a novel type of tripodal amido ligand provides the key to the synthesis of stable M-M' (M = Ti, Zr, Hf; M' = Fe, Ru) heterobimetallic complexes, [MeSi(SiMe(2)N(C(6)H(4)Me-4)}(3)M-M'(eta(5)-C5H5)(CO)(2)] 4-9, with unsupported metal-metal bonds and thus enables systematic studies of these complexes; the crystal structures of the Ti-Fe (4) and Zr-Fe (6) complexes are reported, the latter being the first X-ray structure of a compound containing a Zr-Fe bond; reaction of the M-M' complexes with methyl isocyanide leads to the immediate insertion into the metal-metal bond, a reaction which is analogous to alpha-additions to isocyanides.

  DOI：

  10.1039/cc9960000219

文献信息

• Atom-transfer within the coordination sphere of early–late heterobimetallic complexes: rapid deoxygenation of sulfoxides at low temperatures
  作者：Sylvie Fabre、Bernd Findeis、Dominique J. M. Trösch、Lutz H. Gade、Ian J. Scowen、Mary McPartlin

  DOI：10.1039/a900010k

  日期：——

  Extremely rapid oxygen transfer from sulfoxides to a carbonyl ligand to give the corresponding thioether and coordinated CO2 is observed in the reactions of unsupported Zr–Ru heterodimetallic complexes with sulfoxides; this is interpreted to arise from the cooperative reactivity of the two complementary metal complex fragments bound to each other through a highly polar metal–metal bond.

  在无支撑的锆钌杂二金属络合物与硫氧化物的反应中，观察到氧从硫氧化物极快地转移到羰基配体上，生成相应的硫醚和配位二氧化碳；据解释，这是由于两个互补的金属络合物片段通过高极性金属键相互结合而产生的协同反应性。