mer-Mo(bpy)(CO)3(P(NMeCH2CH2O))(1+) | 168285-62-9

• 英文名称: mer-Mo(bpy)(CO)3(P(NMeCH2CH2O))(1+)
• CAS: 168285-62-9
• 化学式: C₁₆H₁₅MoN₃O₄P
• 分子量: 440.227
• InChiKey: KHSBKJBOGVUCLT-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-methoxy-3-methyl-1,3,2-oxazaphospholidine 、 mer-Mo(bpy)(CO)3(P(NMeCH2CH2O))(1+) 生成 [(2,2'-bipyridine)Mo(CO)2(PN(Me)CH2CH2O)((MeO)PN(Me)CH2CH2O)](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
• 作为产物：
  描述：

  fac-[(2,2'-bipyridine)Mo(CO)3((MeO)PN(Me)CH2CH2O)] 在 BF₃*Et₂O 作用下， 生成 mer-Mo(bpy)(CO)3(P(NMeCH2CH2O))(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

• Cationic Phosphenium Complexes of Group 6 Transition Metals. Systematic Approach to Elucidation of Influence of Substituents of the Phosphenium Phosphorus on the Stability of the Complexes
  作者：Yoshitaka Yamaguchi、Hiroshi Nakazawa、Tomonori Itoh、Katsuhiko Miyoshi

  DOI：10.1246/bcsj.69.983

  日期：1996.4

  OMe)}] (M = Cr, Mo, and W; XY = (NEt2)2, 1a; N(Me)CH2CH2O, 2a; (NEt2)(OMe), 3a; OCMe2CMe2O, 4a; (OMe)2, 5a) have been prepared and subjected to the reaction with BF3·OEt2. In these reactions, cationic phosphenium complexes [(bpy)(CO)3MPXY}]+ are formed by an OMe abstraction as an anion from the phosphorus ligand for 1a, 2a, and 3a (M = Mo, W). The reaction of 3a (M = Cr) yields fac-[(bpy)(CO)3CrP(OMe)2F}]

  第 6 族过渡金属亚磷酸酯络合物，fac-[(bpy)(CO)3MPXY(OMe)}]（M = Cr、Mo 和 W；XY = (NEt2)2, 1a；N(Me)CH2CH2O， 2a; (NEt2)(OMe), 3a; OCMe2CMe2O, 4a; (OMe)2, 5a) 已制备并与 BF3·OEt2 反应。在这些反应中，阳离子鏻络合物 [(bpy)(CO)3MPXY}]+ 是通过 OMe 提取形成的，作为来自 1a、2a 和 3a 的磷配体的阴离子（M = Mo，W）。3a (M = Cr) 的反应生成 fac-[(bpy)(CO)3CrP(OMe)2F}] (Cr-5c) 和 [(bpy)(CO)3CrP(NEt2)F2}] (Cr-7d)。在 4a 和 5a 对所有第 6 组同系物的反应中，发生 OMe/F 取代反应生成 fac-[(bpy)(CO)3MP(OMe)2F}