{Mn(CO)4(dppm)}ClO4 | 78129-33-6

• 英文名称: {Mn(CO)4(dppm)}ClO4
• CAS: 78129-33-6
• 化学式: C₂₉H₂₂MnO₄P₂*ClO₄
• 分子量: 650.827
• InChiKey: GIIIKBSPWSNOAT-UHFFFAOYSA-M

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：

  {Mn(CO)4(dppm)}ClO4 在 KOH 作用下， 以 二氯甲烷 为溶剂， 以87%的产率得到{Mn(CO)4((Ph2P)2CH)}
  参考文献：
  名称：

  Controlled double metalation of coordinated dppm in manganese(I) complexes. The ligand [(PPh2)2C]2- as a building block in the syntheses of heterometallic species

  摘要：

  The cationic complexes fac-[Mn(CNBut)(CO)3(dppm)]ClO4 (1a) and [Mn(CO)4(dPPM)]ClO4 (1b) are readily deprotonated by KOH in CH2Cl2 to give the bis(diphenylphosphino)methanide derivatives fac-[Mn(CNBut)(CO)3{(Ph2P)2CH}] (2a) and [Mn(CO)4{(Ph2P)2CH}] (2b). When 2a and 2b are reacted with [Ag(ClO4)(PPh3)], the heterodimetallic complexes fac-[Mn(CNBut)(CO)3{(Ph2P)2CH(AgPPh3)}]ClO4 (3a) and [Mn(CO)4{(Ph2P)2CH(AgPPh3)}]ClO4 (3b) are obtained. For 3a an X-ray analysis has been carried out. Crystal data: monoclinic, space group P2(1)/c, a = 11.828 (3) angstrom, b = 24.518 (5) angstrom, c = 17.293 (6) angstrom, beta = 94.94 (3)-degrees, V = 4996 (2) angstrom3, Z = 4, R = 0.033, R(w) = 0.036. The heterodimetallic complexes [Mn-(CNBut)(CO)3{(Ph2P)2CH(AuPPh3)}]ClO4 (4a) and [Mn(CO)4{(Ph2P)2CH(AuPPh3)}]ClO4 (4b) have been synthesized by two alternative methods: (a) by treating 1a and 1b with 1 equiv of [AuCI(PPh3)] and an excess of KOH and (b) by reacting 3a and 3b with 1 equiv of [AuCl(PPh3)]. The treatment of 1a and lb with 2 equiv of [AuCI(PPh3)] and an excess of KOH produces the trimetallic species fac-[Mn(CNBut)-(CO)3{(Ph2P)2C(AuPPh3)2}]ClO4 (5a) and [Mn(CO)4{(Ph2P)2C(AuPPh3)2}] (5b), which formally contain the dianion [(PPh2)2C]2-. When 4a is reacted with [AgCl(PPh3)], in the presence of KOH, the mixed heterotrimetallic species [Mn(CNBut)(CO)3{(Ph2P)2C(AgPPh3)(AuPPh3)}]ClO4 (6a) is obtained. A mechanism for the formation of 6a involving the neutral intermediate [Mn(CNBut)(CO)3{(Ph2P)2C(AuPPh3)}] (7) is proposed in agreement with the data obtained in the X-ray analysis of 6a. Crystal data: monoclinic, space group P2(1)/n, a = 14.192 (3) angstrom b = 20.622 (6) angstrom, c = 24.37 (1) angstrom, 94.91 (3)-degrees, V = 7106 (5) angstrom3, Z = 4, R = 0.045, R(w) = 0.044.

  DOI：

  10.1021/om00060a025
• 作为产物：
  描述：

  fac-[(κ₂-dppm)Mn(CO)₃Br] 在 一氧化碳 作用下， 以 二氯甲烷 为溶剂， 生成 {Mn(CO)4(dppm)}ClO4
  参考文献：
  名称：

  锰（I）与二膦的阳离子羰基配合物

  摘要：

  溴羰基化合物fac -BrMn（CO）3（diphos）（diphosPh 2 P（CH 2）n PPh 2（n = 1（dpm），2（dpe），3（dpp）和4（dbp））与AgClO 4在二氯甲烷溶液中反应，得到中性的fac -O 3 ClOMn（CO）3（diphos）。后者的配合物在室温下与各种配体L膦（PR 3），亚磷酸酯（P（OR）3），吡啶（Py），乙腈（MeCN），四氢噻吩（THT）或丙酮（Me 2 CO）导致阳离子种类fac- [Mn（CO）3（diphos）L] ClO 4（或当L = CO时变为[Mn（CO）4（diphos））] ClO 4。当L是磷配体，阳离子FAC -tricarbonyls在加热到异构化聚体异构体，这只能通过该方法DIPHOSDPM中分离，该反应在除此以外的情况下伴随着分解。所述的紫外线照射聚体- [锰（CO）3（DIPHOS）L] CLO

  DOI：

  10.1016/s0022-328x(00)82439-0

文献信息

• Neutral and cationic dicarbonyl complexes of manganese (I) with diphosphines
  作者：G.A. Carriedo、V. Riera、J. Santamaria

  DOI：10.1016/s0022-328x(00)85853-2

  日期：1982.8

  spectroscopy to have one dppm monodentate and the other bidendate. This complex reacts with TIPF6 in dichloromethane solution to give the salt cis-[Mn(CO)2-(dppm)2]PF6 or, if the reaction is carried out in the presence of CO, the salt mer-[Mn(CO)3(dppm)2]PF6 which also has one monodentate dppm (by 31P NMR). The cationic complex cis-[Mn(CO)2(dppm)2]+ isomerizes to the transisomer when irradiated with

  BrMn（CO）5与DPPM在回流的甲苯中反应，得到中性化合物顺式-顺式-BrMn（CO）2（DPPM）2，其通过31 P NMR光谱显示具有一个DPPM单齿和另一个双齿。该配合物与TIPF 6在二氯甲烷溶液中反应，生成顺式[[Mn（CO）2-（DPPM）2 ] PF 6盐；如果该反应在CO的存在下进行，则该盐mer- [Mn（ CO）3（DPPM）2 ] PF 6也具有一个单齿DPPM（乘以31NMR）。阳离子络合物的顺式- [锰（CO）2（DPPM）2 ] +异构化成transisomer当用UV光照射，而后者的加热还给的顺式-异构体。阳离子顺式-[Mn（CO）2（DPPM）2 +的高氯酸盐可以通过使fac -O 3 ClOMn（CO）3（DPPM）与DPPM在回流的甲苯中和反式-[Mn（CO）2通过处理fac -O 3，（diphos）（diphos）'] +，diphos或diph