[fac-Mn(CO)3(1,2-bis(diphenylphosphino)ethane)(OH2)]BF4 | 247939-31-7

• 英文名称: [fac-Mn(CO)3(1,2-bis(diphenylphosphino)ethane)(OH2)]BF4
• 英文别名: fac-[(carbonyl)3(bis(diphenylphosphino)ethan)(water)(manganese(I)] tetrafluoroborate；fac-[(CO)3(dppe)Mn(OH2)]BF4
• CAS: 247939-31-7
• 化学式: BF₄*C₂₉H₂₆MnO₄P₂
• 分子量: 642.213
• InChiKey: HAKMGMCSZIBJPE-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：

  4-氰基吡啶 、 [fac-Mn(CO)3(1,2-bis(diphenylphosphino)ethane)(OH2)]BF4 以 氯仿 为溶剂， 以80%的产率得到K1(NC),K1(N)-[(CO)3(dppe)Mn(4-cyanopyridine)Mn(dppe)Mn(CO)3](tetrafluoroborate)2
  参考文献：
  名称：

  [(CO)3(dppe)Mn(OH2)]BF4 (1). A synthetically versatile compound and its use as a probe for determining the preferred site of coordination on ambident ligands

  摘要：

  Previous work in this laboratory has shown that the Mn(I) octahedral complex, [(CO)(3)(dppe)Mn(OH2)]BF4 (1), may be used for the synthesis of many related complexes by the ready replacement of the aqua ligand by neutral and anionic ligands, leading to new complexes having a variety of functional groups sigma (eta(1)) bonded to the Mn atom. This procedure has now been extended to ligands possessing phenolic and carboxylic acid groups, including amino acids. Compound 1 is used as a probe to compare the relative coordinating ability of different heteroatoms on ambident ligands. The H-1 NMR spectra of the resulting complexes show two signals at room temperature for the four protons (each 2H m) of the dppe-Mn metallacyle whose position depends on the specific atom of the ligand that is attached to the metal. The spectrum of 1, however, shows only one signal (4H m). On cooling to -53 degrees C this signal is split in two (both 2H, in) owing to a slowing of the rapid reversible dissociation of the aqua ligand. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2005.08.032
• 作为产物：
  描述：

  tetrafluoroboric acid 、 [(CO)3 (dppe) (acetate) manganese(I)] 以 氯仿 为溶剂， 生成 [fac-Mn(CO)3(1,2-bis(diphenylphosphino)ethane)(OH2)]BF4 、 溶剂黄146
  参考文献：
  名称：

  [(CO)3(dppe)Mn(OH2)]BF4 (1). A synthetically versatile compound and its use as a probe for determining the preferred site of coordination on ambident ligands

  摘要：

  Previous work in this laboratory has shown that the Mn(I) octahedral complex, [(CO)(3)(dppe)Mn(OH2)]BF4 (1), may be used for the synthesis of many related complexes by the ready replacement of the aqua ligand by neutral and anionic ligands, leading to new complexes having a variety of functional groups sigma (eta(1)) bonded to the Mn atom. This procedure has now been extended to ligands possessing phenolic and carboxylic acid groups, including amino acids. Compound 1 is used as a probe to compare the relative coordinating ability of different heteroatoms on ambident ligands. The H-1 NMR spectra of the resulting complexes show two signals at room temperature for the four protons (each 2H m) of the dppe-Mn metallacyle whose position depends on the specific atom of the ligand that is attached to the metal. The spectrum of 1, however, shows only one signal (4H m). On cooling to -53 degrees C this signal is split in two (both 2H, in) owing to a slowing of the rapid reversible dissociation of the aqua ligand. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2005.08.032

文献信息

• Use of the aqua complex [ fac -Mn(CO) 3 (dppe)OH 2 ]BF 4 for the preparation of a series of fac -Mn(CO) 3 (dppe)Z and [ fac -Mn(CO) 3 (dppe)Z]BF 4 complexes. X-ray crystal structures of three representative examples
  作者：Thomas M. Becker、Jeanette A. Krause Bauer、Craig L. Homrighausen、Milton Orchin

  DOI：10.1016/s0022-328x(00)00130-3

  日期：2000.5

  (prepared by a simple two-step, high-yield synthesis) is readily replaced by the desired anionic ligand Z−, to give a six-coordinate neutral species fac-Mn(CO)3(dppe)Z. Examples of such complexes where ZONO2, CN, OMe, OC(O)OMe, and OS(O)2CF3 (OTf) are reported herein. Neutral ligands also replace the aqua ligand to give ionic complexes [fac-Mn(CO)3(dppe)Z]BF4. Examples where Z=2,6-dimethylphenyl (xylyl)

  在AQUA配体的标题配合物（通过简单的两步，高产率合成制备的）很容易通过所期望的阴离子配体ž取代- ，得到六配位的中性物质FAC -Mn（CO）3（DPPE） Z. 本文报道了其中Z ＝O ＝NO 2，CN，OMe，OC（O）OMe和OS（O）2 CF 3（OTf）的此类络合物的实例。中性配体还取代了水族配体，得到离子络合物[ FAc -Mn（CO）3（DPPE）Z] BF 4。本文还报道了Z ＝ 2，6-二甲基苯基（二甲苯基）异氰化物，乙腈，苄腈和丙烯腈的实例。FAc -Mn（CO）3的晶体结构（DPPE）NO 3（2），[ FAc -Mn（CO）3（DPPE）（二甲苯基-NC）] BF 4（7）和[ FAc-（CO）3 Mn（DPPE）（PhCN）] BF 4（9），报道。
• A novel dimanganese complex linked by an unusually strong hydrogen bond. X-ray structure of the hydrogen-bonded complex and ab initio calculations
  作者：Thomas M Becker、Jeanette A.Krause Bauer、Janet E.Del Bene、Milton Orchin

  DOI：10.1016/s0022-328x(01)00829-4

  日期：2001.6

  3, are held together by an unusually strong O–H⋯F hydrogen bond (O⋯F=2.458(3) Å, H⋯F=1.52 Å) between the aqua ligand on one manganese and the fluoro atom on the other manganese. Using as a simple model the interaction between +Li(H2O) and FLi, the hydrogen bonding distance O–H⋯F was calculated to be; O⋯F=2.443 Å. Authentic 3 was prepared in a homogeneous system using CH2Cl2-soluble [Et4N]F.

  试图通过处理水络合物[（CO）3（dppe）Mn（OH 2）] BF 4（1）的CH 2 Cl 2溶液来制备氟络合物（CO）3（dppe）MnF（3）用NaF （aq）代替，我们分离出二锰配合物[（CO）3（dppe）Mn（OH 2）⋯FMn（dppe）（CO）3 ] BF 4（2）。两个部分1和3通过一个锰上的水配体与另一个锰上的氟原子之间的异常强的O–H⋯F氢键（O⋯F = 2.458（3）Å，H⋯F = 1.52Å）结合在一起。用一个简单的模型+ Li（H 2 O）和FLi之间的相互作用，计算出氢键距离O–H⋯F为：O⋯F ＝ 2.443埃。使用可溶于CH 2 Cl 2的[Et 4 N] F在均质系统中制备Authentic 3。
• Reaction of [fac-(CO)3(dppe)Mn(OH2)]BF4 with 13CO and conversion of the resulting tetracarbonyl to labeled isocyanato complexes
  作者：Thomas M. Becker、Koka Jayasimhulu、Milton Orchin

  DOI：10.1016/s0022-328x(00)00503-9

  日期：2000.9

  When 13CO is bubbled into a CH2Cl2 solution of [fac-(CO)3(dppe)Mn(OH2)]BF4 (dppe=Ph2PCH2CH2PPh2), the aqua ligand is replaced by the CO to give the tetracarbonyl, [(CO)3(13CO)(dppe)Mn]BF4 (1) in which the labeled CO appears exclusively at the site originally occupied by the aqua ligand. Treatment of this aqua complex with NaN3 leads to an approximate 50:50 mixture of isocyanates corresponding to attack

  当将13 CO鼓泡到[ fac-（CO）3（dppe）Mn（OH 2）] BF 4（dppe = Ph 2 PCH 2 CH 2 PPh 2）的CH 2 Cl 2溶液中时，aqua配体被取代生成四羰基[（CO）3（13 CO）（dppe）Mn] BF 4（1）的CO，其中标记的CO仅出现在最初由水配体占据的位点。用NaN 3处理这种水复合物导致大约50:50的异氰酸酯混合物对应于以相等的概率在标记的CO或其轴向配偶体处发生侵蚀。既不两个CO基团的反式在四羰基的P原子都受到影响。