| 132959-05-8

• CAS: 132959-05-8
• 化学式: BF₄*C₄H₈O*C₅₃H₄₅IIrO₃OsP₄
• 分子量: 1522.07
• InChiKey: SBPHRVAHKUPFHF-UHFFFAOYSA-N

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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  IrOs(H)(AuP(C₆H₅)3)(CO)3((C₆H₅)2PCH₂P(C₆H₅)2)2⁽¹⁺⁾*BF₄^(1-) = {IrOs(H)(AuP(C₆H₅)3)(CO)3(((C₆H₅)2P)2CH₂)2}BF₄ 在 iodine 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  含铱和的双膦桥接的异双金属络合物。相邻center中心促进的铱中心桥联双（二苯基膦基）甲烷基团的可逆原位金属化

  摘要：

  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.

  DOI：

  10.1021/om00051a018