[IrCl(bis(diphenylphosphino)methane)2] | 132939-91-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [IrCl(bis(diphenylphosphino)methane)2]
• 英文别名: {IrCl(dppm)2}
• CAS: 132939-91-4
• 化学式: C₅₀H₄₄ClIrP₄
• 分子量: 996.467
• InChiKey: FAYYSTRRNYTGPB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.42
• 重原子数：
  56.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  [IrCl(bis(diphenylphosphino)methane)2] 以 四氢呋喃 为溶剂， 生成 [IrRu(H)(CO)3(μ-CO)(bis(diphenylphosphino)methane)2]
  参考文献：
  名称：

  Dell'Anna, Maria Michela; Trepanier, Steven J.; McDonald, Robert, Organometallics, 2001, vol. 20, p. 88 - 99

  摘要：

  DOI：
• 作为产物：
  描述：

  chloro(1,1-bis(diphenylphosphino)methane)(1,1-bis(diphenylphosphino)methanido)hydridoiridium(III) 以 二氯甲烷 为溶剂， 生成 [IrCl(bis(diphenylphosphino)methane)2]
  参考文献：
  名称：

  膦配体与铱配合物的反应导致C（sp 3）-H键活化

  摘要：

  用短咬合双官能N，P-供体配体1-苄基-2-咪唑基二苯基膦（Ph 2 PBnIm）处理[Ir 2（μ-Cl）2（coe）4 ]（coe =环辛烯）导致氧化加成从苄基到金属的C（sp 3）-H键的化学键形成[IrHCl {Ph 2 P（CHPh）Im}（Ph 2 PBnIm）]（1），已通过X射线研究对其进行了充分表征。相关的配体2-吡啶基二苯基膦（Ph 2 PPy）与[Ir 2（μ-Cl）2（coe）4 ]反应，得到单核铱（I）络合物[IrCl（Ph 2 PPy）2 ]（2），其显示了P，N-螯合和P-配位的配体。博士的加成2 PBnIm至2产生的替换P-协调的Ph 2聚吡咯配体与苄基C-H键除了铱沿开始，得到[IrHCl {博士2 P（CHPh配合）进出口}（PH 2聚吡咯）。该结果表明[IrCl（Ph 2 PBnIm）（L）]类型的单核络合物（L = P，N-螯合配体）是经历CH键活化反应的活性物质。[Ir

  DOI：

  10.1021/om049142i

文献信息

• An iridium-mediated C–H activation/CO2-carboxylation reaction of 1,1-bisdiphenylphosphinomethane
  作者：Jens Langer、María José Fabra、Pilar García-Orduña、Fernando J. Lahoz、Helmar Görls、Luis A. Oro、Matthias Westerhausen

  DOI：10.1039/c0dt00230e

  日期：——

  The reaction of 1,1-bisdiphenylphosphinomethane (dppm, 4 eq.) with [IrCl(coe)2]2 results in a solvent dependent equilibrium from which the complexes [IrCl(dppm)(dppm-H)(H)] (1) and [Ir(dppm)2]Cl (2) were isolated. When 2 is dissolved in methanol, [IrCl(dppm)2(H)][OCH3] (4) is formed as dominant species in solution. The C–H activation reaction which leads to 1 and 4 can be suppressed by adding an additional

  的反应 1,1-双二苯基膦甲烷 （百万分之几，4 eq。）与 [IrCl（coe）2 ] 2 导致溶剂依赖性平衡，复合物[IrCl（DPPM）（DPPM-H）（高）]（1）和[Ir（DPPM）2 ] Cl（2）被隔离。当2溶解在甲醇，[IrCl（DPPM）2（H）] [OCH 3 ]（4）在溶液中形成为主要物质。可以通过添加额外的碳来抑制导致1和4的C–H活化反应。百万分之几 每个配体 铱 中心导致形成 [Ir（DPPM）3 ] Cl（5）。如果反应百万分之几 和 [IrX（coe）2 ] 2 （X = 氯，I）在CO 2气氛下进行[[IrX（DPPM）（H）（Ph 2 P）2 C–COOH}]（6：X =氯; 7：X ＝ I）由CH活化/ CO 2羧化序列形成。的反应6用NH 4 PF收率[的IrCl（DPPM）2（H）] PF 6（10）。另外锂 化合物[Li（dme）2（DPPM-H）]（3）和[Li（dme）（Ph
• Unusual mixed-metal carbonate-bridged complexes via oxidation of a carbonyl ligand in [RhM(CO)4(Ph2PCH2PPh2)2] (M = Mn, Re) and [IrRe(CO)5(Ph2PCH2PPh2)2]
  作者：David M. Antonelli、Martin Cowie

  DOI：10.1021/om00053a020

  日期：1991.7

  The complexes [RhM(CO)4(dppm)2] (M = Mn (1), Re (2); dppm = Ph2PCH2PPh2) and [IrRe(CO)5(dppm)2] (3) react with molecular oxygen to give the corresponding carbonate complexes [RhM(CO)3(mu-CO3)(dppm)2] (M = Mn (4), Re (5)) and [IrRe(CO)3(mu-CO3)(dppm)2] (6). No intermediates were observed in these reactions even at -60-degrees-C. The X-ray structure determination of compound 4 shows that the carbonate ligand bridges the metals in a unique mu-2-eta-2 fashion in which one oxygen atom bridges the metals and another is also bound in Mn leaving one oxygen uncoordinated. Compound 4 crystallizes in the monoclinic space group C2/c with a = 35.591 (6) angstrom, b = 12.556 (3) angstrom, c = 25.277 (5) angstrom, beta = 116.46 (2)-degrees, V = 10112.8 angstrom 3, and Z = 8. The structure, which displays a 70:30 rotationally disordered ''RhMn(CO)3(mu-CO3)'' moiety, has refined to R = 0.079 and R(w) = 0.104 on the basis of 366 parameters refined and 2942 independent observations.
• Diphosphine-bridged, heterobimetallic complexes containing iridium and osmium. Reversible orthometalation of a bridging bis(diphenylphosphino)methane group at the iridium center promoted by the adjacent osmium center
  作者：Robert W. Hilts、Roberta A. Franchuk、Martin Cowie

  DOI：10.1021/om00051a018

  日期：1991.5

  The compound (PPN)[HOs(CO)4] reacts readily with [IrCl(eta-2-dppm)2] (PPN+ = (Ph3P)2N+, dppm = Ph2PCH2PPh2) at ambient temperature, yielding the heterobinuclear complex [IrOs(H)2(CO)3(mu-2-eta-3-(o-C6H4)PhPCH2PPh2)(dppm)] (1), in which one phenyl group is ortho-metalated at the Ir center. Treatment of 1 with the electrophile sources HBF4.Et2O or [AuPPh3]BF4 reverses the ortho metalation to give the hydrido-bridged species, [IrOs(CO)3(mu-H)(mu-X)(dppm)2][BF4] (X = H (2), AuPPh3 (3)). Deprotonation of 2 with use of NaH regenerates compound 1. The AuPPh3 group in 3 is readily replaced by an iodo group in the reaction with I2 to give [IrOs(CO)3(mu-H)(mu-I)(dppm)][TBF4] (4). Under a CO atmosphere, compound 2 yields [IrOs(CO)5(dppm)2][BF4] (5), and reaction of 5 with Me3NO.2H2O results in loss of one carbonyl group from the Ir center to yield [IrOs(CO)4(dppm)2][BF4] (6). The structure of 5 has been determined by X-ray techniques. This compound crystallizes, together with 1.5 equiv of CH2Cl2, in monoclinic space group P2(1)/c, with cell parameters a = 12.063 (2) angstrom, b = 22.725 (3) angstrom, c = 22.050 (3) angstrom, beta = 101.66 (1)-degrees, V = 5920 angstrom-3, and Z = 4. The structure has refined to R = 0.043 and R(w) = 0.043 and R(w) = 0.063 on the basis 5515 unique observations with 444 parameters varied. Compound 5 has a trans-bridging arrangement of diphosphine ligands and has two carbonyls bound to Ir and three on Os. The carbonyl and phosphine arrangement on Os suggests a trigonal bipyramidal (TBP) arrangement characteristic of Os(0), which then forms a dative Os --> Ir bond to the Ir(+I) center, giving it a TBP geometry also. The Os-Ir separation of 2.9652 (4) angstrom is at the long end of the range expected for a normal single bond.