[MeSi(SiMe2N(p-tolyl))3ZrCl] | 162898-60-4

• 英文名称: [MeSi(SiMe2N(p-tolyl))3ZrCl]
• CAS: 162898-60-4
• 化学式: C₂₈H₄₂ClN₃Si₄Zr
• 分子量: 659.681
• InChiKey: YSOOQZCRARIOHR-UHFFFAOYSA-M

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：

  lithium phenylacetylide 、 [MeSi(SiMe2N(p-tolyl))3ZrCl] 以 乙醚 为溶剂， 以96%的产率得到[[bis[dimethyl-(4-methylphenyl)azanidylsilyl]-methylsilyl]-dimethylsilyl]-(4-methylphenyl)azanide;ethynylbenzene;zirconium(4+)
  参考文献：
  名称：

  Tripodal amido-titanium and -zirconium complexes containing a trisilylsilane-derived ligand framework

  摘要：

  A series of amido-titanium and -zirconium complexes containing a tripodal amide with a trisilylsilane ligand framework has been prepared. The primary isolable products in the reaction of SiMe (SiMe(2)NHR)(3) (R = 4-MeC(6)H(4), 2-FC6H4 or 4-MeOC(6)H(4)) with LiBu(n) and ZrCl4 in diethyl ether are the [Li(OEt(2))(2)Cl] adducts of which the five-co-ordinate complex [{(4-MeOC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu Cl)(2)Li(OEt(2))(2)] and the six-co-ordinate [{(2-FC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu-Cl)(2)Li(OEt(2))(2)] have been characterised by X-ray crystallography. In the latter one of the fluorine atoms of the peripheral 2-FC6H4 groups is weakly coordinated to the metal. Stirring of the (Et(2)O)(2)LiCl adducts in toluene generates the four-co-ordinate complexes [Zr{SiMe(SiMe(2)NR)(3)}Cl]. Upon reaction of [M{SiMe[SiMe(2)N(C6H4F-2)](3)}Cl] (M = Ti or Zr) with AgO3SCF3 the corresponding triflates were obtained which are sufficiently stable to be isolated, The halide ligand may be readily substituted to give the corresponding methyl, ethynyl and cyclopentadienyl complexes.

  DOI：

  10.1039/dt9960000125
• 作为产物：
  描述：

  以 甲苯 为溶剂， 生成 [MeSi(SiMe2N(p-tolyl))3ZrCl]
  参考文献：
  名称：

  Tripodal amido-titanium and -zirconium complexes containing a trisilylsilane-derived ligand framework

  摘要：

  A series of amido-titanium and -zirconium complexes containing a tripodal amide with a trisilylsilane ligand framework has been prepared. The primary isolable products in the reaction of SiMe (SiMe(2)NHR)(3) (R = 4-MeC(6)H(4), 2-FC6H4 or 4-MeOC(6)H(4)) with LiBu(n) and ZrCl4 in diethyl ether are the [Li(OEt(2))(2)Cl] adducts of which the five-co-ordinate complex [{(4-MeOC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu Cl)(2)Li(OEt(2))(2)] and the six-co-ordinate [{(2-FC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu-Cl)(2)Li(OEt(2))(2)] have been characterised by X-ray crystallography. In the latter one of the fluorine atoms of the peripheral 2-FC6H4 groups is weakly coordinated to the metal. Stirring of the (Et(2)O)(2)LiCl adducts in toluene generates the four-co-ordinate complexes [Zr{SiMe(SiMe(2)NR)(3)}Cl]. Upon reaction of [M{SiMe[SiMe(2)N(C6H4F-2)](3)}Cl] (M = Ti or Zr) with AgO3SCF3 the corresponding triflates were obtained which are sufficiently stable to be isolated, The halide ligand may be readily substituted to give the corresponding methyl, ethynyl and cyclopentadienyl complexes.

  DOI：

  10.1039/dt9960000125

文献信息

• Ti−Sn, Zr−Sn, and Hf−Sn Heterodimetallic Complexes:  Stabilizing Unsupported Group 4−Group 14 Metal−Metal Bonds
  作者：Matthias Lutz、Bernd Findeis、Matti Haukka、Tapani A. Pakkanen、Lutz H. Gade

  DOI：10.1021/om010114z

  日期：2001.6.1

  Reaction of the tripodal amido complexes [MeSiSiMe2N(4-CH3C6H4)}3ZrCl] and [MeSiSiMe2N(4-CH3C6H4)}3HfCl] with LiSnPh3 in toluene yielded the Zr−Sn and Hf−Sn complexes [MeSiSiMe2N(4-CH3C6H4)}3ZrSnPh3] (1) and [MeSiSiMe2N(4-CH3C6H4)}3HfSnPh3] (2), while attempts to synthesize the corresponding Ti−Sn complex resulted in the oxidative coupling of the stannate to give Ph3Sn−SnPh3 and unidentified titanium

  三脚架酰胺配合物[MeSi SiMe 2 N（4-CH 3 C 6 H 4）} 3 ZrCl]和[MeSi SiMe 2 N（4-CH 3 C 6 H 4）} 3 HfCl]与LiSnPh 3的反应在甲苯中生成Zr-Sn和Hf-Sn络合物[MeSi SiMe 2 N（4-CH 3 C 6 H 4）} 3 ZrSnPh 3 ]（1）和[MeSi SiMe 2 N（4-CH 3 C 6） H 4）} 3 HfSnPh[3 ]（2），尽管试图合成相应的Ti-Sn配合物导致锡酸盐的氧化偶合，从而得到Ph 3 Sn-SnPh 3和未鉴定的钛物质。通过三酰胺基锡酸盐配合物[MeSi SiMe 2 N（4-CH 3 C 6 H 4）} 3 SnLi（OEt 2）]与茂金属二氯化物[Cp 2 MCl 2 ]的所有三种钛族金属，得到[MeSi SiMe 2 N（4-CH 3 C 6 H 4）} 3SNM（η
• Synthesis and Reactivity of Early−Late Heterodinuclear Complexes Stabilized by a Trisilylsilane-Based Tripodal Amido Ligand
  作者：Lutz H. Gade、Martin Schubart、Bernd Findeis、Sylvie Fabre、Izoldi Bezougli、Matthias Lutz、Ian J. Scowen、Mary McPartlin

  DOI：10.1021/ic990562n

  日期：1999.11.1

  The reaction of the complexes [MeSiSiMe2N(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 [MeSiSiMe2N(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 [MeSiSiMe2N(p-tol)}(3)M-M'(CO)(2)Cp] (M. M': Ti, Fe (3); Ti, Ru (4); Zr, Fe (5)) and [MeSiSiMe2N(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 [MeSiSiMe2N(R)}(3)Meta(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 [MeSiSiMe2N(p-tol)}(3)Tieta(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)ZrOS(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.
• Schubart, Martin; Findeis, Bernd; Gade, Lutz H., Chemische Berichte, 1995, vol. 128, # 4, p. 329 - 334
  作者：Schubart, Martin、Findeis, Bernd、Gade, Lutz H.、Li, Wan-Sheung、McPartlin, Mary

  DOI：——

  日期：——
• 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
  作者：Bernd Findeis、Martin Schubart、Christina Platzek、Lutz H. Gade、Ian Scowen、Mary McPartlin

  DOI：10.1039/cc9960000219

  日期：——

  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.