[Re(nitrosyl)2(tricyclohexylphosphine)2(CCH)] | 1189393-05-2

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: [Re(nitrosyl)2(tricyclohexylphosphine)2(CCH)]
• CAS: 1189393-05-2
• 化学式: C₃₈H₆₇N₂O₂P₂Re
• 分子量: 832.117
• InChiKey: YZUNQRQDASJYPA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  tetrakis[3,5-bis(trifluoromethyl)phenyl]boric acid bis(diethyl ether) complex 、 [Re(nitrosyl)2(tricyclohexylphosphine)2(CCH)] 以 二氯甲烷 为溶剂， 以97%的产率得到[Re(nitrosyl)2(tricyclohexylphosphine)2(CCH2)][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]
  参考文献：
  名称：

  Reactivity of Cationic Dinitrosyl Bisphosphine Rhenium Complexes toward Acetylene: Base-Controlled Product Formation

  摘要：

  Reactions of the dinitrosyl bisphosphine rhenium cations [Re(NO)(2)(PR3)(2)][BAr4F] (R = Cy 1a; R = iPr 1b [BAr4F](-) = tetrakis[(3,5-bis(trifluoromethyl)phenyl)borate]) with acetylene yielded the alkvnyl (o-vinyl)hydroxylamido nitrosyl bisphosphine complexes [Re(CH=C(H)ONH)(C CH)-(NO)(PR3)(2)][BAr4F] (3a and 3b) in the absence of base, while in the presence of 2,6-di(tertbutyl)pyridine formation of the neutral alkynyl complexes (Re(C CH)(NO)(2)(PR3)(2)] (4a and 4b) was observed. A plausible mechanism is presented and supported by various NMR techniques, IR spectroscopy, and DFT calculations. Treatment of 4a and 4b with [H(OEt2)(2)][BAr4F] gave the corresponding vinylidene complexes [Re(C=CH2)(NO)(2)(PR3)(2)][BAr4F] (5a and 5b) in high yields, which only slowly convert into the alkynyl(o-vinyl)hydroxylamido nitrosyl bisphosphine complexes 3a and 3b when treated with a large excess of acetylene. Thiophenol or benzeneselenol underwent 1,2-additions onto the vinylidene ligands of 5a and 5b to yield the cationic Fischer-type carbene complexes [Re(C(XPh)CH3)(NO)(2)(PR3)(2)][BAr4F] (X = S 6a,b; X = Se 7a,b) quantitatively. X-ray diffraction studies were carried out oil 4b, 5b, and 7a.

  DOI：

  10.1021/om9003412
• 作为产物：
  描述：

  [Re(nitrosyl)2(tricyclohexylphosphine)2][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate] 、 乙炔 在 2,6-di(tert-butyl)pyridine 作用下， 以 苯 为溶剂， 以83%的产率得到[Re(nitrosyl)2(tricyclohexylphosphine)2(CCH)]
  参考文献：
  名称：

  Reactivity of Cationic Dinitrosyl Bisphosphine Rhenium Complexes toward Acetylene: Base-Controlled Product Formation

  摘要：

  Reactions of the dinitrosyl bisphosphine rhenium cations [Re(NO)(2)(PR3)(2)][BAr4F] (R = Cy 1a; R = iPr 1b [BAr4F](-) = tetrakis[(3,5-bis(trifluoromethyl)phenyl)borate]) with acetylene yielded the alkvnyl (o-vinyl)hydroxylamido nitrosyl bisphosphine complexes [Re(CH=C(H)ONH)(C CH)-(NO)(PR3)(2)][BAr4F] (3a and 3b) in the absence of base, while in the presence of 2,6-di(tertbutyl)pyridine formation of the neutral alkynyl complexes (Re(C CH)(NO)(2)(PR3)(2)] (4a and 4b) was observed. A plausible mechanism is presented and supported by various NMR techniques, IR spectroscopy, and DFT calculations. Treatment of 4a and 4b with [H(OEt2)(2)][BAr4F] gave the corresponding vinylidene complexes [Re(C=CH2)(NO)(2)(PR3)(2)][BAr4F] (5a and 5b) in high yields, which only slowly convert into the alkynyl(o-vinyl)hydroxylamido nitrosyl bisphosphine complexes 3a and 3b when treated with a large excess of acetylene. Thiophenol or benzeneselenol underwent 1,2-additions onto the vinylidene ligands of 5a and 5b to yield the cationic Fischer-type carbene complexes [Re(C(XPh)CH3)(NO)(2)(PR3)(2)][BAr4F] (X = S 6a,b; X = Se 7a,b) quantitatively. X-ray diffraction studies were carried out oil 4b, 5b, and 7a.

  DOI：

  10.1021/om9003412