trans-[(2,2'-bipyridine)Cr(CO)2(P(N(Me)CH2)2)((MeO)P(N(Me)CH2)2)](1+) | 168285-60-7

• 英文名称: trans-[(2,2'-bipyridine)Cr(CO)2(P(N(Me)CH2)2)((MeO)P(N(Me)CH2)2)](1+)
• CAS: 168285-60-7
• 化学式: C₂₁H₃₁CrN₆O₃P₂
• 分子量: 529.459
• InChiKey: LBSZJKMDYHYSBE-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

• 作为产物：
  描述：

  mer-{chromium(2,2'-bipyridine)(tricarbonyl)(1,3-dimethyl-1,3,2-diazaphospholane-2-yl)}(1+) 、 2-methoxy-1,3-dimethyl-1,3,2-diazaphospholane 以 二氯甲烷 为溶剂， 生成 trans-[(2,2'-bipyridine)Cr(CO)2(P(N(Me)CH2)2)((MeO)P(N(Me)CH2)2)](1+)
  参考文献：
  名称：

  Cationic Phosphenium Complexes of Group 6 Transition Metals: Reactivity, Isomerization, and X-ray Structures

  摘要：

  The reaction of cationic diamino-substituted phosphenium complexes of group 6 transition metals mer-[(bpy)(CO)(3)M{PN(Me)CH(2)CH(2)NMe}](+) (M = Cr, Mo, W) with L (L = PN(Me)CH(2)CH(2)NMe(OR) (R = Me, Et), PPh(3)) proceeds with substitution of L for CO to produce [(bpy)(CO)(2)LM{PN(Me)CH(2)CH(2)NMe}](+). During the reaction, the phosphenium ligand remains intact. The product consists of trans (two phosphorus ligands are mutually trans) and cis isomers, and they equilibrate. The cis form is electronically and the traits form is sterically favored. A similar reaction takes place when cationic monoamino-substituted phosphenium complexes are treated. Complexes trans-[(bpy)(CO)(2){PN(Me)CH(2)CH(2)NMe(OMe)}Mo{PN(Me)CH(2)CH(2)NMe}]-OTf (trans-2a-OTf) (OTf = SO3 CF3) and trans-[(phen)(CO)(2){PN(t-Bu)CH2CH2O(OMe)}Mo{PN(t-Bu)CH2CH2O}]-OTf-CH2Cl2 (trans-2j-OTf-CH2Cl2) have been characterized by X-ray diffraction. The bond distance of Mo-P(phosphenium) is significantly shorter than that of Mo-P(phosphite) for both complexes: for trans-2a, 2.254 Angstrom vs 2.495 Angstrom and, for trans-2j, 2.238 Angstrom vs 2.529 Angstrom, indicating a significant double bond character between Mo and P(phosphenium). For both complexes, the P-N bond distances in phosphenium and in phosphite ligands are almost equal, indicating that there is no significant N --> P(phosphenium) pi donation. The role of the amino groups on the phosphenium phosphorus is probably to protect the approach of a nucleophile to phosphenium phosphorus by high p pi lone pair density flanking the phosphenium center.

  DOI：

  10.1021/om00009a020

文献信息

• Reactivity of Cationic Transition-Metal Phosphenium Complexes
  作者：Hiroshi Nakazawa、Yoshitaka Yamaguchi、Katsuhiko Miyoshi

  DOI：10.1080/10426509608545107

  日期：——

  phosphenium complexes has been investigated. Reaction of mer-[(bpy)(CO)3MPN(Me)CH2CH2NMe}]+ (M = Cr, Mo, W) with X−(X = Me, OEt) exhibits a nucleophilic attack at the phosphenium phosphorus, whereas that with L (L = phosphine, phosphite) shows CO/L substitution. Iron phosphenium complexes, [Cp(CO)RFe-PN(Me)CH2CH2NMe}]+ undergoes a migratory insertion of the phosphenium ligand into the Fe-alkyl bond

  摘要 研究了阳离子过渡金属鏻配合物的反应性。mer-[(bpy)(CO)3MPN(Me)CH2CH2NMe}]+ (M = Cr, Mo, W) 与 X−(X = Me, OEt) 的反应表现出对鏻磷的亲核攻击，而与 L (L = 膦，亚磷酸盐) 显示 CO/L 取代。铁鏻配合物 [Cp(CO)RFe-PN(Me)CH2CH2NMe}]+ 经历鏻配体迁移插入 Fe-烷基键。