(C5Me5)W(CO)2(κ2(C,N)-C(Me)NSiEt3) | 949030-63-1

• 英文名称: (C5Me5)W(CO)2(κ2(C,N)-C(Me)NSiEt3)
• 英文别名: [(η5-C5Me5)(CO)2W[κ2C,N-C(Me)=N(SiEt3)]]
• CAS: 949030-63-1
• 化学式: C₂₀H₃₃NO₂SiW
• 分子量: 531.423
• InChiKey: ZKYDQNBKMWGRPB-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  (C5Me5)W(CO)2(κ2(C,N)-C(Me)NSiEt3) 、 乙腈 以 氘代苯 为溶剂， 生成 (C5Me5)W(CO)2(κ2(C,N)-C(Me)NC(Me)NH)
  参考文献：
  名称：

  Three- and Five-Membered W/C/N Metallacycles Formed by Incorporation of Acetonitrile Molecules into Silyltungsten Intermediates

  摘要：

  Treatment of Cp*(CO)(2)W(NCMe)Me (Cp* = eta(5)-C5Me5) with HSiR3 (R = Et, p-Tol) afforded N-silylated eta(2)-iminoacyl tungsten complexes Cp*(CO)(2)W{kappa(2)(C,N)-C(Me)N(SiR3)} (1a, R = Et; 1b, R = p-Tol). Analogous reactions in the presence of excess acetonitrile for a prolonged reaction time led to the formation of five-membered metallacycles Cp*(CO)(2)W{kappa(2)(C,N)-C(Me)N-C(Me)N(H)} (2) and Cp*(CO)(2)W{kappa(2)(C,N)-C(CH2SiR3)N-C(Me)N(H)} (3, R = p-Tol) through a C-N coupling of nitrile molecules and migration of a silyl group.

  DOI：

  10.1021/om700514d
• 作为产物：
  描述：

  三乙基硅烷 、 [(η⁵-C₅Me₅)(CO)₂W(NCMe)Me] 以 乙腈 为溶剂， 以74%的产率得到(C5Me5)W(CO)2(κ2(C,N)-C(Me)NSiEt3)
  参考文献：
  名称：

  Three- and Five-Membered W/C/N Metallacycles Formed by Incorporation of Acetonitrile Molecules into Silyltungsten Intermediates

  摘要：

  Treatment of Cp*(CO)(2)W(NCMe)Me (Cp* = eta(5)-C5Me5) with HSiR3 (R = Et, p-Tol) afforded N-silylated eta(2)-iminoacyl tungsten complexes Cp*(CO)(2)W{kappa(2)(C,N)-C(Me)N(SiR3)} (1a, R = Et; 1b, R = p-Tol). Analogous reactions in the presence of excess acetonitrile for a prolonged reaction time led to the formation of five-membered metallacycles Cp*(CO)(2)W{kappa(2)(C,N)-C(Me)N-C(Me)N(H)} (2) and Cp*(CO)(2)W{kappa(2)(C,N)-C(CH2SiR3)N-C(Me)N(H)} (3, R = p-Tol) through a C-N coupling of nitrile molecules and migration of a silyl group.

  DOI：

  10.1021/om700514d

文献信息

• Synthesis and Characterization of κ²<i>C,N</i>-<i>N</i>-Silyliminoacyl Tungsten Complexes Cp*(CO)₂W{κ²<i>C,N</i>-C(R)═NSiR′₃} [R = Me, Et, <i>i</i>-Pr, <i>t</i>-Bu; R′₃ = (<i>p</i>-Tol)₂Me, (<i>p</i>-Tol)₃, Et₃; Cp* = η⁵-C₅Me₅]: Thermally Induced Carbon−Carbon Bond Cleavage of Their Iminoacyl Ligands
  作者：Eiji Suzuki、Takashi Komuro、Yuto Kanno、Masaaki Okazaki、Hiromi Tobita

  DOI：10.1021/om901123w

  日期：2010.4.12

  complexes Cp*(CO)2W(p-Tol)═Si(p-Tol)R′·DMAP} [1a, R′ = Me; 1b, R′ = p-Tol; DMAP = 4-(dimethylamino)pyridine] reacted with excess nitrile RCN (R = Me, Et, i-Pr, t-Bu) in toluene to give κ2C,N-N-silyliminoacyl tungsten complexes Cp*(CO)2Wκ2C,N-C(R)═NSi(p-Tol)2R′} (2a, R = Me, R′ = Me; 2b, R = Et, R′ = Me; 2c, R = i-Pr, R′ = Me; 2d, R = t-Bu, R′ = Me; 3a, R = Me, R′ = p-Tol; 3b, R = Et, R′ = p-Tol;

  DMAP稳定的（对甲苯基）（亚甲硅烷基）配合物Cp *（CO）2 W（p -Tol）═Si（p -Tol）R'·DMAP} [ 1a，R'= Me; 1b，R'＝p- Tol；DMAP = 4-（二甲基氨基）吡啶]用过量的腈RCN（R =甲基，乙基，反应我-Pr，吨-Bu）的甲苯，得到κ 2 C，N - Ñ -silyliminoacyl钨络合物的Cp *（CO）2 W κ 2 C，N -C（R）═NSi（p -Tol）2 R'}（2a中，R = Me中，R'=甲基;图2b，R =的Et，R'=甲基;图2c，R =i -Pr，R'= Me; 2d，R ＝t- Bu，R′＝ Me；3a，R ＝ Me，R′＝p- Tol；3b，R ＝ Et，R′＝p- Tol；3c，R ＝i- Pr，R′＝p- Tol；3d，R ＝t- Bu，R'＝p- Tol）。该反应通过对甲苯基的1，2-从钨中心向亚