Ni(C5Me5)(μ-η(2),η(2)-C(Me)C(Me)C(O))W(CO)2(C5H4Me) | 167285-93-0

• 英文名称: Ni(C5Me5)(μ-η(2),η(2)-C(Me)C(Me)C(O))W(CO)2(C5H4Me)
• CAS: 167285-93-0
• 化学式: C₂₃H₂₈NiO₃W
• 分子量: 595.014
• InChiKey: XVAGJTJYOVTUNY-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：

  Ni(C5Me5)(μ-η(2),η(2)-C(Me)C(Me)C(O))W(CO)2(C5H4Me) 、 trimethoxonium tetrafluoroborate 以 二氯甲烷 为溶剂， 生成 [Ni(C5Me5)(μ-η(2)(1,3-W),η(3)-(Ni)-C(Me)C(Me)C(OMe))W(CO)2(C5H4Me)]BF4
  参考文献：
  名称：

  Reactions of 2-Butyne with Group 6-Group 10 Heterobimetallics. New Mixed-Metal Metallacycle Chemistry

  摘要：

  The reactions of disubstituted alkynes with the mixed-metal complexes NiCp*M(CO)(3)Cp (1, M = Mo, W) are presented, and the chemistry of the resultant products is developed. Complexes 1 react with nonterminal alkynes to afford nickelacyclic products of the type NiCp*{mu-eta(2)(1,3-Ni),eta(2)(1,2-M)-C(R)C(R')C(O)}M(CO)(2)Cp '' (3) [M = Mo, W; R = R' = Me; R = Me, R' = Ph. Cp '' = Cp, Cp'; not all combinations made]. Complexes 3 may be thermally decarbonylated to the mu-alkyne (dimetallatetrahedrane) complexes NiCp*(mu-eta(2),eta(2)-RC(2)R')M(CO)(2)Cp '' (2). Complex 3a (R = R' = Me; M = Mo; Cp '' = Cp) may be protonated or alkylated at the metallacyclic acyl-like carbonyl ligand with HBF4 . Et(2)O or R(3)O(+)BF(4)(-) (R = Me, Et), respectively, to afford the cationic species [NiCp*{mu-eta(2)(1,3-Mo),eta(2)(1,2-Ni)-C(Me)C(OH)} Mo(CO)(2)Cp](BF4-)-B-+ (4, Ni-Mo) and [NiCp*{mu-eta(2)(1,3-Mo),eta(2)(1,2-Ni)-C(Me)C(Me)C(OR)}Mo(CO)(2)Cp](+) BF4- (Ni-Mo; 5a, R = Me; 5b, R = Et), respectively. On the basis of an analysis of the C-13 NMR spectrum of 5c', a Ni-W analog of 5a, complexes 4 and 5 are believed to contain molybdenacycle, not nickelacycle, rings-i.e. a ''ring flip'' takes place during the protonation or the alkylation reaction. The attempted substitution of a carbonyl ligand in 5a with (t)BuNC in the presense of the oxidant Me(3)NO led to oxidation at the molybdenum center, loss of all carbonyl ligands, rupture of the Ni-Mo bond, and insertion of an isocyanide ligand into one of the Mo-C sigma-bonds. The structure of the resulting cationic molybdenum oxo species 7, NiCp*(mu-eta(3)(1,2,3-Ni)-C(OMe)C(Me)C(Me)C(N(t)Bu)}Mo(O)Cp(+)BF(4)(-) was established by an X-ray diffraction study. Crystal data for 7, NiMoC26H38BF4NO2: monoclinic, P2(1)/c(No. 14), a = 12.288(3) Angstrom, and b = 13.130(2) Angstrom, c = 17.013(4) Angstrom, beta = 93.47 (1)degrees, Z = 4, R(F)= 0.042, and R(w)(F) = 0.051. Complex 5a reacts with KHBEt(3) affording what is believed to be the hydridoacyl species NiCp*(mu-eta(3)(1,2,3-Ni),eta(2)(1,4-Mo)-C(OMe)C(Me)C(Me)C(O)}MoH(CO)Cp (8, NiMo). A carbonyl ligand in 5a may be substituted with an iodide ion to afford the neutral molybdenum iodo species NiCp*(mu-eta(3)-(Ni),eta(2)(1,3-Mo)-C(Me)C(Me)C(OMe)}MoI(CO)Cp (9, Ni-Mo). Alkylation of 9 with MeLi afforded the very air-sensitive Mo-Me complex NiCp*{mu-eta(3)-(Ni>,eta 2(1,3-Mo)-C(Me)C(Me)C(OMe)}MoMe(CO)Cp (10, Ni-Mo).

  DOI：

  10.1021/om00006a044
• 作为产物：
  描述：

  2-丁炔 、 Ni(η(5)-C5Me5)W(CO)3(η(5)-C5H4Me) 以 二氯甲烷 为溶剂， 以90%的产率得到Ni(C5Me5)(μ-η(2),η(2)-C(Me)C(Me)C(O))W(CO)2(C5H4Me)
  参考文献：
  名称：

  Reactions of 2-Butyne with Group 6-Group 10 Heterobimetallics. New Mixed-Metal Metallacycle Chemistry

  摘要：

  The reactions of disubstituted alkynes with the mixed-metal complexes NiCp*M(CO)(3)Cp (1, M = Mo, W) are presented, and the chemistry of the resultant products is developed. Complexes 1 react with nonterminal alkynes to afford nickelacyclic products of the type NiCp*{mu-eta(2)(1,3-Ni),eta(2)(1,2-M)-C(R)C(R')C(O)}M(CO)(2)Cp '' (3) [M = Mo, W; R = R' = Me; R = Me, R' = Ph. Cp '' = Cp, Cp'; not all combinations made]. Complexes 3 may be thermally decarbonylated to the mu-alkyne (dimetallatetrahedrane) complexes NiCp*(mu-eta(2),eta(2)-RC(2)R')M(CO)(2)Cp '' (2). Complex 3a (R = R' = Me; M = Mo; Cp '' = Cp) may be protonated or alkylated at the metallacyclic acyl-like carbonyl ligand with HBF4 . Et(2)O or R(3)O(+)BF(4)(-) (R = Me, Et), respectively, to afford the cationic species [NiCp*{mu-eta(2)(1,3-Mo),eta(2)(1,2-Ni)-C(Me)C(OH)} Mo(CO)(2)Cp](BF4-)-B-+ (4, Ni-Mo) and [NiCp*{mu-eta(2)(1,3-Mo),eta(2)(1,2-Ni)-C(Me)C(Me)C(OR)}Mo(CO)(2)Cp](+) BF4- (Ni-Mo; 5a, R = Me; 5b, R = Et), respectively. On the basis of an analysis of the C-13 NMR spectrum of 5c', a Ni-W analog of 5a, complexes 4 and 5 are believed to contain molybdenacycle, not nickelacycle, rings-i.e. a ''ring flip'' takes place during the protonation or the alkylation reaction. The attempted substitution of a carbonyl ligand in 5a with (t)BuNC in the presense of the oxidant Me(3)NO led to oxidation at the molybdenum center, loss of all carbonyl ligands, rupture of the Ni-Mo bond, and insertion of an isocyanide ligand into one of the Mo-C sigma-bonds. The structure of the resulting cationic molybdenum oxo species 7, NiCp*(mu-eta(3)(1,2,3-Ni)-C(OMe)C(Me)C(Me)C(N(t)Bu)}Mo(O)Cp(+)BF(4)(-) was established by an X-ray diffraction study. Crystal data for 7, NiMoC26H38BF4NO2: monoclinic, P2(1)/c(No. 14), a = 12.288(3) Angstrom, and b = 13.130(2) Angstrom, c = 17.013(4) Angstrom, beta = 93.47 (1)degrees, Z = 4, R(F)= 0.042, and R(w)(F) = 0.051. Complex 5a reacts with KHBEt(3) affording what is believed to be the hydridoacyl species NiCp*(mu-eta(3)(1,2,3-Ni),eta(2)(1,4-Mo)-C(OMe)C(Me)C(Me)C(O)}MoH(CO)Cp (8, NiMo). A carbonyl ligand in 5a may be substituted with an iodide ion to afford the neutral molybdenum iodo species NiCp*(mu-eta(3)-(Ni),eta(2)(1,3-Mo)-C(Me)C(Me)C(OMe)}MoI(CO)Cp (9, Ni-Mo). Alkylation of 9 with MeLi afforded the very air-sensitive Mo-Me complex NiCp*{mu-eta(3)-(Ni>,eta 2(1,3-Mo)-C(Me)C(Me)C(OMe)}MoMe(CO)Cp (10, Ni-Mo).

  DOI：

  10.1021/om00006a044