Mn(1,2-bis(diphenylphosphino)ethane)2(CO)(Br) | 37523-66-3

• 英文名称: Mn(1,2-bis(diphenylphosphino)ethane)2(CO)(Br)
• 英文别名: trans-Mn(CO)(κ2-Ph2PCH2CH2PPh2)2Br；trans-Mn(CO)(κ2-dpe)2Br
• CAS: 37523-66-3；1403665-52-0
• 化学式: C₅₃H₄₈BrMnOP₄
• 分子量: 959.701
• InChiKey: RFMCZSFXDYHOOZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 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：

  Mn(1,2-bis(diphenylphosphino)ethane)2(CO)(Br) 、 lithium aluminium tetrahydride 以 四氢呋喃 为溶剂， 以73%的产率得到Mn(1,2-bis(diphenylphosphino)ethane)2(CO)(H)
  参考文献：
  名称：

  含二膦配体的锰配合物与侧链胺的合成，结构和反应

  摘要：

  将侧基胺配体PN R P（PN R P = Ph 2 PCH 2 NRCH 2 PPh 2 ; R = Me，Ph，n -Bu）加到Mn（CO）5 Br中得到fac -Mn（PN R P）（一氧化碳）3 Br。dppm [dppm = 1,2-双（二苯基膦基）甲烷]对fac -Mn（PN R P）（CO）3 Br的光解提供了混合的双（二膦）配合物，反式-Mn（PN R P）（dppm）（ CO）（溴）。的反应反式-Mn（PN [R带的LiAlH P）（DPPM）（CO）（BR）4通向反式-Mn（PN R P）（dppm）（CO）（H），已通过晶体学表征。Mn（P 2 Ph N 2 Bn）（dppm）（CO）（H）[P 2 Ph N 2 Bn = 1,5-二苯基-3,7-二苄基-1,5-二氮杂-3,7-二磷酸环辛烷]可以用类似的方式制备；它的结构在椅子构造中具有一个螯合环，在船构造中具有第二

  DOI：

  10.1021/om100668e
• 作为产物：
  描述：

  五羰基溴化锰(I) 、 二氯甲烷 、 1,2-双(二苯基膦)乙烷 以 甲苯 为溶剂， 生成 Mn(1,2-bis(diphenylphosphino)ethane)2(CO)(Br) 、 trans-[Mn(CO)2(κ2-Ph2PCH2CH2PPh2)2]Br*0.5dichloromethane
  参考文献：
  名称：

  电子转移和化学反应相关的与单核配合物的一系列广泛的氧化[M（CO）2（κ 1 -PP）（κ 2 -PP）X]和双核配合物[{M（CO）2（κ 2 - PP）X} 2（μ-PP）]（M = Mn，Re; PP =二膦或相关配体; X = Cl，Br）

  摘要：

  广泛的一系列的电化学氧化顺式，聚体-M（CO）2（κ 1 -dpm）（κ 2 -PP）X（M =锰中，Re; DPM =苯基2 PCH 2 PPH 2 ; PP = DPM， Ph 2 PCH 2 CH 2 PPh 2（dpe），o-（Ph 2 P）2 C 6 H 4（dpbz）; X = Cl，Br）络合物已在伏安法和本体电解时间尺度上进行了研究。在短时域或低温下，锰配合物经历可逆的单电子氧化成顺式，二聚体- [锰（CO）2（κ 1 -dpm）（κ 2 -PP）X] +。慢扫描速率伏安条件下这些化合物异构化在室温下，得到的反式- [锰（CO）2（κ 1 -dpm）（κ 2 -PP）X] +，其在甚至更长的本体电解时间尺度慢慢失去X -以形成反应性的反式- [锰（CO）2（κ 2 -dpm）（κ 2 -PP）] 2+中间体。反过来，该络合物在电极表面（X = Cl）或在均相化学反应（X =

  DOI：

  10.1021/om034388t

文献信息

• Cationic Manganese(I) Dihydrogen and Dinitrogen Complexes Derived from a Formally 16-Electron Complex with a Bis-Agostic Interaction, [Mn(CO)(Ph₂PC₂H₄PPh₂)₂]⁺
  作者：Wayne A. King、Xiao-Liang Luo、Brian L. Scott、Gregory J. Kubas、Kurt W. Zilm

  DOI：10.1021/ja960499q

  日期：1996.1.1

  precursor [Mn(CO)(dppe)sub 2}]BAr`sub 4} (1) capable of binding small molecules (dppe = Phsub 2}PCsub 2}Hsub 4}PPhsub 2}; BAr`sub 4} = B[Csub 6}Hsub 3}(3,5-CFsub 3})sub 2}]sub 4}). This species has yielded the first well-characterized cationic manganese-Hsub 2} complex, [Mn(Hsub 2})(CO)(dppe)sub 2}]BAr`sub 4}. The complexes MnHsub 3}(Rsub 2}PCsub 2}Hsub 4}PRsub 2})sub 2} [R = Me (dmpe)

  我们合成了一种新的 16 电子前体 [Mn(CO)(dppe)sub 2}]BAr`sub 4} (1) 能够结合小分子 (dppe = Phsub 2}PCsub 2}H sub 4}PPhsub 2}; BAr`sub 4} = B[Csub 6}Hsub 3}(3,5-CFsub 3})sub 2}]sub 4}) . 该物种产生了第一个表征良好的阳离子锰-Hsub 2} 复合物，[Mn(Hsub 2})(CO)(dppe)sub 2}]BAr`sub 4}。提出复合物 MnHsub 3}(Rsub 2}PCsub 2}Hsub 4}PRsub 2})sub 2} [R = Me (dmpe), Et (depe)] Hsub 2} 配体和 CpMn(CO)sub 2}(Hsub 2}) 最近被分离出来。我们还报告说，Nsub 2}
• Reversible Displacement of Polyagostic Interactions in 16e [Mn(CO)(R₂PC₂H₄PR₂)₂]⁺ by H₂, N₂, and SO₂. Binding and Activation of η²-H₂ trans to CO Is Nearly Invariant to Changes in Charge and cis Ligands
  作者：Wayne A. King、Brian L. Scott、Juergen Eckert、Gregory J. Kubas

  DOI：10.1021/ic981263l

  日期：1999.3.1

  Electrophilic 16e [Mn(CO)(R2PC2H4PR2)(2)](+) complexes (R = Et, Ph) are synthesized by metathesis of MnBr(CO)(R2PC2H4PR2)(2) with Na or Li salts of low-coordinating baron or gallium anions (e.g., [BC6H3(3,5-CF3)(2)}(4)](-) or [Ga(C6F5)(4)](-)). They contain weak polyagostic interactions that are reversibly displaced by H-2, N-2, and SO2 (which is a surprisingly weak ligand here). The agostic aid H-2 complexes, as well as the gallium anions including the new species [Ga(C6F5)(3)}(2)(mu-Cl)](-), have been characterized by NMR, IR, and X-ray crystallography. The agostic Mn-H distances (e.g., 2.9 Angstrom) are much longer than those found for the single agostic interactions in Mo(CO)(diphosphine)(2) and [Mn(CO)(3)(PCy3)(2)](+). The H-H and also the Mn-H distances have been determined in the H-2 complex by T-1 measurements for both the H-2 and HD isotopomers. IR data and C-O and M-C bond lengths are used to gauge the pi-acceptor strengths of ligands trans to the CO. The agostic C-H bonds are the weakest ligands and also the weakest accepters, but the H-2 ligand is an excellent acceptor as strong as N-2 and ethylene. The variation of nu(CO) on increasing the basicity of the cis-phosphine (dppe versus depe) in trans-M(CO)(diphosphine)(2)(L) is less than expected and far less than that on increasing the charge on the complex (M = Mn+ versus Mo). The H-H bond lengths (0.87-0.90 Angstrom) and J(HD) NMR couplings (32-34 Hz) in [Mn(CO)(R2PC2H4PR2)(2)(H-2)](+) and other cationic H-2 complexes with trans-CO are strikingly similar to their neutral analogues and nearly invariant. Activation of H-H in the more electrophilic cationic systems occurs primarily via increased a donation from H-2 as compared to the more electron-rich neutral analogues where back-bonding dominates. The nature of the ligand trans to H-2 (the strong acceptor CO here) controls the H-H distance more so than all of the cis ligands combined, especially fbr cationic complexes.