([2-[(dimethylamino)methyl]phenyl]hydrosilanediyl)chromium(0) pentacarbonyl | 148538-99-2

• 英文名称: ([2-[(dimethylamino)methyl]phenyl]hydrosilanediyl)chromium(0) pentacarbonyl
• 英文别名: [[[2-(dimethylamino)methyl]phenyl]silanediyl]chromium(0) pentacarbonyl；2-{(dimethylamino)methyl}phenylsilanediylchromium(0) pentacarbonyl
• CAS: 148538-99-2
• 化学式: C₁₄H₁₃CrNO₅Si
• 分子量: 355.342
• InChiKey: TWFGSMAOZNBEFH-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：

  ([2-[(dimethylamino)methyl]phenyl]hydrosilanediyl)chromium(0) pentacarbonyl 、 三苯基氯甲烷 以 二氯甲烷 、 甲苯 为溶剂， 以65%的产率得到[[2-((dimethylamino)methyl)phenyl]chlorosilanediyl]chromium(0) pentacarbonyl
  参考文献：
  名称：

  Base Stabilization of Functionalized Silylene Transition Metal Complexes

  摘要：

  The dehydrogenative coupling reaction of primary silanes ArSiH3 [Ar = [2-(Me(2)NCH(2))C6H4], [8-(Me(2)NCH(2))C10H6], [8-(Me(2)N)C6H4]] with Fe(CO)(5), Cr(CO)(6), CpCo(CO)(2), and RCpMn(CO)(3) (R = H, CH3) under photolytic conditions affords an effective access to intramolecular base-stabilized functionalized silanediyl-transition metal complexes of general formula [ArHSi=MLn]. Si-29-NMR investigations of the photochemical reaction of PhSiH(3) with Fe(CO)(5) in the presence of 1,3-dimethyl-2-imidazolidinone (DMI) or hexamethylphosphoric triamide indicates a two-step mechanism for the formation of base-stabilized silanediyl-transition metal complexes. The carbonyl displacement reactions of the complex [2-(Me(2)-NCH2)C6H4]HSi=Cr(CO)(5) in the presence of PPh(3) or P(OMe)(3) lead to the formation of trans-(PPh(3))(2)Cr(CO)(4) or trans-[P(OMe)(3)]Cr-2(CO)(4), respectively, either by photolysis or by thermolysis. Photochemical displacement reaction with (diphenylphosphino)ethane furnished [2-(Me(2)NCH(2))C6H4]HSi=Cr[Ph(3)(CH2)(2)PPh(2)](CO)(3) by subsequent displacement of two carbonyls of the metal moiety. Exchange reactions of the complex [2-(Me(2)NCH(2))C6H4]HSi=Cr(CO)(5) with Ph(3)CX (X = Cl, BF4, OSO2CF3) or CH(3)COX' (X' = Cl, Pr) provide a direct entry to a series of functionalized complexes [2-(Me(2)NCH(2))C6H4]XSi=Cr(CO)(5). The liberated silylenes from complexes ArHSi(B)=Fe(CO)(4) (Ar = Ph, 1-Np) (B = DMI) can be trapped in the presence of tert-butyl alcohol or methanol to give di-tert-butoxysilanes or trimethoxysilanes, respectively.

  DOI：

  10.1021/om00004a019
• 作为产物：
  描述：

  2-[(dimethylamino)methyl]phenyltrihydrosilane 、 六羰基铬 以 正戊烷 为溶剂， 以87%的产率得到([2-[(dimethylamino)methyl]phenyl]hydrosilanediyl)chromium(0) pentacarbonyl
  参考文献：
  名称：

  Base Stabilization of Functionalized Silylene Transition Metal Complexes

  摘要：

  The dehydrogenative coupling reaction of primary silanes ArSiH3 [Ar = [2-(Me(2)NCH(2))C6H4], [8-(Me(2)NCH(2))C10H6], [8-(Me(2)N)C6H4]] with Fe(CO)(5), Cr(CO)(6), CpCo(CO)(2), and RCpMn(CO)(3) (R = H, CH3) under photolytic conditions affords an effective access to intramolecular base-stabilized functionalized silanediyl-transition metal complexes of general formula [ArHSi=MLn]. Si-29-NMR investigations of the photochemical reaction of PhSiH(3) with Fe(CO)(5) in the presence of 1,3-dimethyl-2-imidazolidinone (DMI) or hexamethylphosphoric triamide indicates a two-step mechanism for the formation of base-stabilized silanediyl-transition metal complexes. The carbonyl displacement reactions of the complex [2-(Me(2)-NCH2)C6H4]HSi=Cr(CO)(5) in the presence of PPh(3) or P(OMe)(3) lead to the formation of trans-(PPh(3))(2)Cr(CO)(4) or trans-[P(OMe)(3)]Cr-2(CO)(4), respectively, either by photolysis or by thermolysis. Photochemical displacement reaction with (diphenylphosphino)ethane furnished [2-(Me(2)NCH(2))C6H4]HSi=Cr[Ph(3)(CH2)(2)PPh(2)](CO)(3) by subsequent displacement of two carbonyls of the metal moiety. Exchange reactions of the complex [2-(Me(2)NCH(2))C6H4]HSi=Cr(CO)(5) with Ph(3)CX (X = Cl, BF4, OSO2CF3) or CH(3)COX' (X' = Cl, Pr) provide a direct entry to a series of functionalized complexes [2-(Me(2)NCH(2))C6H4]XSi=Cr(CO)(5). The liberated silylenes from complexes ArHSi(B)=Fe(CO)(4) (Ar = Ph, 1-Np) (B = DMI) can be trapped in the presence of tert-butyl alcohol or methanol to give di-tert-butoxysilanes or trimethoxysilanes, respectively.

  DOI：

  10.1021/om00004a019

文献信息

• Corriu, Robert J. P.; Lanneau, Gérard F.; Chauhan, Bhanu P. S., Organometallics, 1993, vol. 12, # 6, p. 2001 - 2003
  作者：Corriu, Robert J. P.、Lanneau, Gérard F.、Chauhan, Bhanu P. S.

  DOI：——

  日期：——
• Handwerker, Hermann; Leis, Christian; Probst, Reiner, Organometallics, 1993, vol. 12, # 6, p. 2162 - 2176
  作者：Handwerker, Hermann、Leis, Christian、Probst, Reiner、Bissinger, Peter、Grohmann, Andreas、Kiprof, Pavlo、Herdtweck, Eberhardt、Blümel, Janet、Auner, Norbert、Zybill, Christian

  DOI：——

  日期：——
• Unexpected Reactivity of Functionalized Lewis Base Stabilized Silanediyl Transition Metal Complexes toward Organolithium Nucleophiles
  作者：Robert J. P. Corriu、Bhanu P. S. Chauhan、Gerard F. Lanneau

  DOI：10.1021/om00008a056

  日期：1995.8

  (Organosilanediyl)chromium(0) pentacarbonyl complexes, [2-(Me(2)NCH(2))C6H4]RSi=Cr(CO)(5) (R = Me, Ph, t-Bu, Ph-C=C-, Me(3)Si-C=C-), are obtained in good yield through the coupling reactions of (arylhydrogenosilanediyl)chromium(0) pentacarbonyl complex [2-(Me(2)NCH(2))C6H4]HSi=Cr(CO)(5), with the corresponding organolithium nucleophiles. Unexpectedly, the chloro- and bromosilanediyl complexes [2-(Me(2)NCH(2))C6H4]XSi=Cr(CO)(5) (X = Cl, Pr) are unreactive, but the fluorosilanediyl complex is even, more reactive than, the hydrogenosilanediyl complex with methyllithium. Possible geometries of the intermediate resulting in frontside attach of the nucleophile upon a zwitterionic silicon species are discussed.