[Re(CO)3Br{κ²-P,P′-bis(diphenylphosphino)ethane}] | 57298-40-5

• 英文名称: [Re(CO)3Br{κ²-P,P′-bis(diphenylphosphino)ethane}]
• 英文别名: fac-[ReBr(CO)3(bis(diphenylphosphino)ethane)]；(fac-(1,2-bis(diphenylphosphino)ethane)tricarbonyl rhenium(I)) bromide；fac-Re(CO)3(dppe)Br；fac-Re(CO)3((Ph2PCH2)2)Br；fac-Re(CO)3(Ph2PCH2CH2PPh2)Br；fac-Re(CO)3(dpe)Br
• CAS: 57298-40-5
• 化学式: C₂₉H₂₄BrO₃P₂Re
• 分子量: 748.566
• InChiKey: AARXDEHJYASMNL-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：

  [Re(CO)3Br{κ²-P,P′-bis(diphenylphosphino)ethane}] 、 silver tetrafluoroborate 在 CO 作用下， 以 二氯甲烷 为溶剂， 以89%的产率得到((1,2-bis(diphenylphosphino)ethane)tetracarbonyl rhenium(I))BF4
  参考文献：
  名称：

  The synthesis and reactions of ReI carboxylic acids. The X-ray structure of fac-Re(CO)3(dppp)CO2D·0.5C6D6

  摘要：

  The metallocarboxylic acids Re(CO)3(P-P)C(O)OH where (P-P) is either dppe [1,2-bis(diphenylphosphino)ethane] or dppp [1,3-bis(diphenylphosphino)propane] and their deuterio analogs have been prepared from the reaction of [Re(CO)4(P-P)]+ BF4- with NaOH(D) and characterized. Concentrated benzene solutions of the dppp complex deposit the acid as a dimer with 1 mol of solvated benzene and the X-ray crystal structure study of the deuterio dimer acid is reported. The cationic salts, 1, do not react with alcohols unless base is present. However, the acids are immediately esterified when they are dissolved in alcohols by virtue of the acids' spontaneous ionization through acyl-oxygen cleavage to the cation and hydroxyl anion; the latter abstracts a proton to give the conjugate base of the alcohol required for esterification. Solutions of the acids in DMSO undergo slow decarboxylation to the corresponding hydrides; addition of KOH to either DMSO or DMF solutions results in immediate decarboxylation.

  DOI：

  10.1016/0022-328x(92)80053-z
• 作为产物：
  描述：

  五羰基溴铼(I) 、 1,2-双(二苯基膦)乙烷 以 氯仿 为溶剂， 生成 [Re(CO)3Br{κ²-P,P′-bis(diphenylphosphino)ethane}]
  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

• Oligophosphan-Liganden XLII. Carbonyl(cyclopentadienyl)rhenium(I)-Komplexe η1-C5H5Re(CO)3L2 mit fluktuierender sp3- und starrer sp2-Koordination des C5H5-Rings
  作者：Lutz Dahlenburg、Gabriele Hillmann、Markus Ernst、Matthias Moll、Falk Knoch

  DOI：10.1016/s0022-328x(96)06503-5

  日期：1996.11

  allowed to interact with Na[Ca5H5] in THF. Treatment of 18 with Na[C5H5] produced fac-η1-C5H5Re(CO)3[C5H8(PCy2)2] as a mixture of three isomers with the rhenium atom in the allylic position of a fluxional sp3-bonded ring (25a) or in the two vinylic sites of an sp2-bonded rigid C5H5 sytem, where the CH2 group is either α or β to the metalated carbon atom (25b, 25c), η5-C5H5Re(CO)3 and fac-[Re(CO)3(Ph2PCH2PPh2-P

  卤rh（I）配合物的混合物fac-Re（CO）3 L 2 X（L / X = PMe 3 / Br（1），PPh 3 / Cl（2）PCy 3 / Br（3）），fac- Re（CO）3（Ph 2 PCH 2 PPh 2）Br，4 fac-Re（CO）3 [R 2 P（CH 2）2 PR 2 ] Br（RMe（5），Ph（6），Cy （7）），fac-Re（CO）3 [Ph 2 P（CH 2）3 PPh2 ] Cl，8和fac-Re（CO）3 [C 5 H 8（PCy 2）2 ] Br，9（C 5 H 8（PCy 2）2 = rac，反式-环戊烷-1,2-二基-双（二环己基）膦）与Ag [O 3 SCF 3 ]生成fac-Re（CO）3（PR 3）2 OSO 2 CF 3（RMe（10），Ph（11），Cy（12） ），fac-Re（CO）3 [R 2P（CH 2）n PR 2 ] OSO
• Coordination chemistry of the tetraphenyldithioimidodiphosphinate ligand [Ph2P(S)NP(S)Ph2]− and Ph2P(CH2)nPPh2, n = 1, 2, 3 toward ReBr(CO)5
  作者：María Obdulia Sánchez-Guadarrama、David Martínez-Velázquez、Noé Zúñiga-Villarreal

  DOI：10.1016/j.ica.2018.12.024

  日期：2019.3

  coordination chemistry of diphosphines dppe, dppm, and dppp towards [Re(CO)4κ2-S,S′-Ph2P(S)NP(S)Ph2}] was explored. The four types of new complexes prepared depicted monocoordination of the diphosphine or the Ph2P(S)NP(S)Ph2 ligands, bridging diphosphine ligands, and dicoordination to afford the spiro complexes. Characterizations were achieved by IR, mass, NMR (1H, 13C, 31P) spectroscopies, and single-crystal

  摘要探讨了二膦类化合物dppe，dppm和dppp对[Re（CO）4 κ2-S，S'-Ph2P（S）NP（S）Ph2}]的配位化学。制备的四种新型复合物描述了二膦或Ph2P（S）NP（S）Ph2配体的单配位，桥接二膦配体和二配位以提供螺环配合物。通过IR，质谱，NMR（1H，13C，31P）光谱学和单晶X射线衍射进行表征。
• Electronic Communication in Luminescent Dicyanorhenate-Bridged Homotrinuclear Rhenium(I) Complexes
  作者：Yelan Xiao、Apple Wai-Yi Cheung、Sze-Wing Lai、Shun-Cheung Cheng、Shek-Man Yiu、Chi-Fai Leung、Chi-Chiu Ko

  DOI：10.1021/acs.inorgchem.9b00072

  日期：2019.5.20

  cyano-bridged homotrinuclear Re(I) complexes with the general formula of [Re]′[Re][Re]′}+ [Re]′ = −[ReI(CO)2(LL)(X)]; [Re] = −[(NC)ReI(CO)2(phen)(CN)]–; LL = diimine, diphosphine, or two carbonyl ligands; X = triphenylphosphine or carbonyl ligand} and the corresponding mononuclear complex analogues were synthesized. The structures of most of the trinuclear Re(I) complexes have been determined by X-ray

  通式为[Re]'[Re] [Re]'} + [Re]'=-[Re I（CO）2（LL）（X））的一系列氰基桥联同核三价Re（I）配合物）]; [Re] =-[（NC）Re I（CO）2（phen）（CN）] –；LL =二亚胺，二膦或两个羰基配体；X ＝三苯基膦或羰基配体}和相应的单核络合物类似物。大多数三核Re（I）配合物的结构已通过X射线晶体学确定。在这些结构中，外围相对于中心Re（I）单元的相对方向变化很大。这些三核Re（I）配合物的光物理性质已得到检验。具有Br 2的三核Re（I）配合物除外phen配体，所有其他三单元组都显示橙色或红色的光致发光，这些发光来自中央Re（I）单元的3 MLCT [dπ（Re）→π*（phen）]，这表明外围发色团与分子之间有效的能量转移中央单元。除了这些三核配合物中Re（I）生色团之间的有效能量转移过程外，[NC-Re-CN]桥联配体在the金属中心之间进行电子偶联的能力还通过ca
• The synthesis of alkoxycarbonyl, carbamoyl and isocyanato complexes, fac-M(CO)3(P-P)Z [M = Mn, Re; P-P = dppe, dppp; Z = C(O)OMe, C(O)OEt, C(O)NHPrn, NCO]. The single crystal structures of fac-Mn(CO)3(dppp)C(O)OEt and fac-Mn(CO)3(dppe)NCO
  作者：Santosh K. Mandal、Douglas M. Ho、Milton Orchin

  DOI：10.1016/s0277-5387(00)83162-9

  日期：1992.1

  The title compounds were prepared by the reaction of the cationic complex [M(CO)4(P-P)]+[BF4]- With the appropriate nucleophiles leading to fac-M(CO)3(P-P)Z [M = Mn, Re; P-P = dppe, dppp; Z = C(O)OMe, C(O)OEt, C(O)NHPrn, NCO] complexes. The X-ray structures of fac-Mn(CO)3(dppp)C(O)OEt and fac-Mn(CO)3(dppe)NCO are also reported.
• 1,2-Metallotropic shifts in tricarbonylrhenium(I) complexes of pyridazine (pydz): a dynamic NMR investigation of the effects of cis-chelating ligands
  作者：Edward W. Abel、Peter J. Heard、Keith G. Orrell

  DOI：10.1016/s0020-1693(96)05339-x

  日期：1997.2

  Complexes of general formula fac-[Re(CO)(3)(L-L)(pydz)][BF4] (L-L=neutral bidentate chelate ligand; pydz=pyridazine) were prepared in high yield from fac-[ReBr(CO)(3)(L-L)]. The pyridazine ligand coordinates to the metal moiety in a monodentate fashion, and undergoes a facile intramolecular 1,2-Re-N shift. The kinetics of the 1,2-metallotropic shift were measured by either one-dimensional NMR bandshape analysis or two-dimensional exchange spectroscopy. The free energies of activation, Delta G(not equal) (298 K), were found to be dependent on the nature of the chelate ligand, and were in the range 77-87 kl mol(-1). The origins of the chelate ligand effects are discussed.