[Mn(CO)3(3,5-di-tert-butylcatecholate)*PPh3](1-) | 134078-44-7

• 英文名称: [Mn(CO)3(3,5-di-tert-butylcatecholate)*PPh3](1-)
• CAS: 134078-44-7
• 化学式: C₃₅H₃₅MnO₅P
• 分子量: 621.572
• InChiKey: MLTKHTPSHVTREK-UHFFFAOYSA-L

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

• 作为产物：
  描述：

  3,5-二叔丁基邻苯醌 以 二氯甲烷 为溶剂， 生成 [Mn(CO)3(3,5-di-tert-butylcatecholate)*PPh3](1-)
  参考文献：
  名称：

  Nucleophilic attack at the five-coordinate anion [Mn(CO)3(3,5-di-tert-butyl-catecholate)]− controlled by electronic and steric effects

  摘要：

  The five-coordinate anion [Mn(CO)(3)(DBCat)](-)has been found to undergo nucleophilic CO substitution reactions with L = PR3, P(OR)(3) producing the dicarbonyl derivatives [Mn(CO)(2)(L)(DBCat)](-). The reaction yield is higher for better nucleophiles such as L = PEt3 and P(OEt)(3); the latter species reacts quantitatively even when added in an equivalent amount. Contrary to this, bully phosphines with the cone angle theta greater than or equal to 145 degrees, namely L = PPh3, PCy3, do not show this reaction but interact reversibly with [Mn(CO)(3)(DBCat)](-) at low temperatures to give the six-coordinate adducts [Mn(CO)(3)(DBCat). L](-). For L = pyridine the corresponding adduct is already formed at room temperature. Similarly, [Mn(CO)(2){P(OEt)(3)} (DBCat)](-) takes up reversibly P(OEt)(3). The spectroscopic and redox properties of the adducts closely correspond with those of the invariably six-coordinate anions [Re(CO)(4-n)(L)(n)(DBCat)](-) (n=1, 2). The uptake of a Lewis base by [Mn(CO)(3)(DBCat)](-) is facilitated by an electrophilic attack at the oxygen lone pairs of the sigma,pi-donor DBCat ligand. Examples are the anions [Mn(CO)(3)(L) (DBCat . BF3)](-) (L = THF, PPh3) and [Mn(CO)(3)(PPh3) (DBCat . CS,)](-) which an inherently stable at ambient temperature. This reactivity is closely related to the DBCat-localized le oxidation of [Mn(CO)(3)(DBCat)](-) producing six-coordinate radicals [Mn(CO)(3)(L)(DBSQ)]. The electrophilic attack of CS2 at the DBCat ligand has also been documented by the conversion of [Mn(CO)(3)(DBCat)](-) in the absence of PPh3 to the trithiocarbonate complex [Mn(CO)(4)(S2CS)](-) and uncoordinated 4,6-di-tert-butyl-1,3-benzdioxol-2-thione. (C) 1998 Elsevier Science S.A.

  DOI：

  10.1016/s0020-1693(97)05627-2