fac-[Mn(OClO3)(CO)3(1,2-bis(diphenylphosphino)ethane)] | 78099-96-4

• 英文名称: fac-[Mn(OClO3)(CO)3(1,2-bis(diphenylphosphino)ethane)]
• 英文别名: fac-tricarbonyl(dppe)(perchlorato)manganese；fac-[Mn(OClO3)(CO)3(Ph2PCH2CH2PPh2)]
• CAS: 78099-96-4
• 化学式: C₂₉H₂₄ClMnO₇P₂
• 分子量: 636.844
• InChiKey: DPFPQGFMKZYJHN-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：

  fac-[Mn(OClO3)(CO)3(1,2-bis(diphenylphosphino)ethane)] 在 C₂H₄(P(C₆H₅)2)2 作用下， 以 二氯甲烷 为溶剂， 以89%的产率得到trans-{Mn(CO)2(dpe)2}ClO4
  参考文献：
  名称：

  锰与二膦的中性和阳离子二羰基配合物

  摘要：

  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

  DOI：

  10.1016/s0022-328x(00)85853-2
• 作为产物：
  描述：

  silver perchlorate 、 fac-[bromo(1,2-bis(diphenylphosphino)ethane)tricarbonylmanganese(I)] 以 二氯甲烷 为溶剂， 以70-80的产率得到fac-[Mn(OClO3)(CO)3(1,2-bis(diphenylphosphino)ethane)]
  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

• Cationic di- and mono-carbonyl complexes of manganese(I)
  作者：G.A. Carriedo、J. Gimeno、M. Laguna、V. Riera

  DOI：10.1016/0022-328x(81)85010-3

  日期：1981.10

  The complexes fac-O3ClOMn(CO)3(NN) (NN = 1,10-phenantroline (phen) or 2,2'bipyridine (bipy)) react with an excess of the ligands L [L = P(OR)3 or P(OR)2Ph, R = Me or Et] in refluxing ethanol to give cis-trans-[Mn(CO)2-(NN)L2]ClO4, or the more highly substituted [Mn(CO)(NN)L3]ClO4 if the reaction is carried out under UV irradiation. Carbonylation at normal pressure of the latter complexes results in

  配合物fac -O 3 ClOMn（CO）3（NN）（NN = 1,10-菲咯啉（phen）或2,2'bipyridine（bipy））与过量的配体L [L = P（OR）3或P（OR）2 Ph，R = Me或Et]在回流的乙醇中制得顺-反式-[Mn（CO）2-（NN）L 2 ] ClO 4，或取代度更高的[Mn（CO） （NN）L 3 ] ClO 4，如果反应在UV辐射下进行。后者配合物在常压下的羰基化导致顺-顺-[Mn（CO）2（NN）L 2 ] ClO 4的形成在丙酮中加热时会发生异构化为顺反异构体。
• NHC–manganese(i) complexes as carbene transfer agents
  作者：Javier Ruiz、Ángela Berros、Bernabé F. Perandones、Marilín Vivanco

  DOI：10.1039/b906450h

  日期：——

  Tautomerization of coordinated azoles to their corresponding N-heterocyclic carbenes (NHCs) has been carried out by reaction of complexes fac-[Mn(L)(CO)3(dppe)]+ (L = N-phenylimidazole) and fac-[Mn(L)(CO)3(bipy)]+ (L = N-methylbenzimidazole, benzoxazole, benzothiazole) with KOtBu and subsequent protonation of the azolyl intermediates with NH4PF6. Several NHC–manganese(I) complexes bearing an N–H residue of general formula fac-[Mn(NHC)(CO)3(dppe)]+ and fac-[Mn(NHC)(CO)3(bipy)]+ have been tested as carbene transfer agents to the gold fragments [Au(L)]+ (L = PPh3, CNPh, CNXylyl), allowing isolation or spectroscopic detection of various Mn(I)/Au(I) heterometallic intermediates containing azolyl bridging ligands, which liberate the gold(I) carbene complexes [Au(NHC)(L)]+ by means of acid hydrolysis. By contrast, when using the silver(I) fragment [Ag(PPh3)]+ as carbene acceptor no transmetallation process occurred but instead inverse tautomerization of the NHC to the corresponding imidazole ligand was observed.

  通过配合物 fac-[Mn(L)(CO)3(dppe)]+ （L = N-苯基咪唑）和 fac-[Mn(L)(CO)3(bipy)]+（L = N-甲基苯并咪唑、和 fac-[Mn(L)(CO)3(bipy)]+（L = N-甲基苯并咪唑、苯并恶唑、苯并噻唑）与 KOtBu 反应，然后用 NH4PF6 使唑基中间体质子化。一些含有通式为 fac-[Mn(NHC)(CO)3(dppe)]+ 和 fac-[Mn(NHC)(CO)3(bipy)]+ 的 NHCâmanganese(I) 复合物带有 NâH 残基，已作为碳烯转移剂对金片段 [Au(L)]+ （L = PPh3、CNPh、CNXylyl）进行了测试、CNXylyl）的碳烯转移剂，从而可以分离或通过光谱检测各种含有偶氮桥配体的 Mn(I)/Au(I)杂金属中间体，这些中间体通过酸水解作用释放出金(I)碳烯配合物 [Au(NHC)(L)]+。与此相反，当使用银（I）片段 [Ag(PPh3)]+ 作为碳烯接受体时，并没有发生透金属化过程，而是观察到 NHC 反向共聚成相应的咪唑配体。
• Cationic carbonyl complexes of manganese(I) with diphenylphosphine
  作者：G.A. Carriedo、V. Riera、M.L. Rodríguez、J.J. Sainz-Velicia

  DOI：10.1016/s0277-5387(00)81099-2

  日期：1987.1

  complexes [Mn(CO) 6− n (PHPh 2 ) n ]ClO 4 , for n = 1 to 4 and [Mn(CO) 4− n (L⌢L)(PHPh 2 ) n ]A (L⌢L = dppm or dppe, n = 1, A = ClO 4 ; L⌢L = bipy or phen, n = 1 or 2, A = ClO 4 or PF 6 ) have been prepared from PHPh 2 and Mn(OClO 3 ) (CO) 5 or fac -MnX(CO) 3 (L⌢L) respectively (X = Br or OClO 3 ). The fac -tricarbonyls fac -[Mn(CO) 3 (PHPh 2 ) 3 ]ClO 4 and fac -[Mn(CO) 3 (L⌢L)(PHPh 2 )]ClO 4 for L⌢L =

  摘要阳离子络合物[Mn（CO）6− n（PHPh 2）n] ClO 4，对于n = 1至4和[Mn（CO）4− n（L⌢L）（PHPh 2）n] A（L由PHPh 2和Mn（OClO 3）制备L = dppm或dppe，n = 1，A = ClO 4； L biL = bipy或phen，n = 1或2，A = ClO 4或PF 6） （CO）5或fac -MnX（CO）3（L⌢L）（X = Br或OClO 3）。当L⌢L= dppm或dppe时，fac-三羰基fac-[Mn（CO）3（PHPh 2）3] ClO 4和fac-[Mn（CO）3（L⌢L）（PHPh 2）] ClO 4，加热至相应的巯基三聚体异构化，二羰基顺式-[Mn（CO）2（PHPh 2）4] ClO 4在紫外线照射下得到反式异构体。
• Miguel, Daniel; Riera, Victor; Miguel, Jesus A., Journal of the Chemical Society, Dalton Transactions
  作者：Miguel, Daniel、Riera, Victor、Miguel, Jesus A.、Diego, Fernando、Bois, Claudette、Jeannin, Yves

  DOI：——

  日期：——
• Synthesis and electrochemistry of polymeric complexes with cationic manganese carbonyl fragments coordinated to polyphosphazenes through nitrile ligands
  作者：Gabino A. Carriedo、Lucía Fernández-Catuxo、Francisco J. García Alonso、Paloma Gómez-Elipe

  DOI：10.1016/0022-328x(95)05540-6

  日期：1995.11

  The cyclotriphosphazenes N3P3(O-C6H4-R-4)(5)(O-C6H4-CN-4), R = H(1a) or (t)Bu(1b), reacted with trans-[MnBr(CO)(2)(dppm) P(OPh)(3)}] and TIPF6 in dichloromethane to give the monocationic complexes [N3P3(O-C(6)H(4)R-4)(5)(O-C6H4-CN)}Mn(CO)(2)(dppm) P(OPh)(3)}][PF6], R=H(2a) or (t)Bu(2b). Similarly, the hexafunctionalized cyclotriphosphazene N3P3(O-C6H4-CN-4)(6) (4) reacted in CH2Cl2 with trans-[MnBr(CO)(2)(dppm)P(OPh)(3)}] in the presence of TIPF6, and with fac-[Mn(OClO3)(CO)(3)(PP)](PP = dppm or dppe), to give the hexacationic complexes [N3P3(O-C6H4-CN)Mn(CO)(2)(dppm)[P(OPh)(3)]}][PF6](6) (5a), [N3P3(O-C6H4-CN)Mn(CO)(3)(PP)}(6)]-(ClO4)(6) (PP = dppm, 6a, or dppe, 6b). In all cases, the changes in the P-31 P NMR chemical shifts for the phosphorus of the phosphazene ring, the molar conductivities in acetone solution and the cyclic voltammograms in CH2Cl2 of the complexes containing the trans-Mn(CO)(2)(dppm)[P(OPh)3] moiety showed a good correlation with the number of metal-carbonyl units bonded to the phosphazene in the mono- and hexa-cationic complexes. Similarly, the nitrile-containing phosphazene polymers NP(O-C6H5)(2-x)(O-C6H4-CN-4)(x)}(n) (x = 0.06, 7a; x = 0.28, 7b), reacted with the corresponding manganese carbonyls to give the complexes NP(O-C6H5)(2-x)[O-C6H4-CNMn(Co)(2)(dppm)P(OPh)(3)}(pF(6))](x)}(n) (x = 0.06, 8a; x = 0.28, 8b) and NP(O-C6H5)(1.94)[O-C6H4-CNMn(CO)(3)(dppe)(ClO4)](0.06)}(n) (9).The cyclic voltammogram of the polymers 8a and 8b in CH2Cl2 showed a very extended oxidation wave with large Delta E(p).