| 165193-92-0

• CAS: 165193-92-0；165307-21-1
• 化学式: CF₃O₃S*C₆₀H₅₀IIr₂O₂P₄
• 分子量: 1587.37
• InChiKey: UTRGCSIOXAIKEV-UHFFFAOYSA-L

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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  、 苯乙炔 以 二氯甲烷 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  阳离子亚乙烯基桥连的配合物及其与炔烃的反应，可生成炔基和亚乙烯基桥连或双（亚乙烯基）产物。末端和桥接亚乙烯基键合模式之间的便捷相互转化

  摘要：

  Reaction of the cationic A-frame complex [Ir-2(CO)(2)(mu-I)(dppm)(2))][SO3CF3] (2) (dppm = Ph2PCH(2)PPh(2)) with either acetylene or phenylacetylene at -78 degrees C yields the respective species [Ir-2(CO)(HCCR)(mu-I)(mu-CO)(dppm)(2)][SO3CF3] (R = H, Ph), in which the alkyne is terminally bound to one metal. At ambient temperature these alkyne adducts slowly rearrange to the vinylidene-bridged species [Ir-2(CO)(2)(mu-I)(mu-CC(H)R)(dppm)(2)][SO3CF3]. An analogous allene adduct is obtained in the reaction of 2 with allene. Reaction of the neutral, vinylidene-bridged complexes [Ir2I2(CO)(2)(mu-CC(H)R)(dppm)(2)] (R = H, Ph) with methyl triflate yields the same cationic vinylidene-bridged species through loss of CH3I. Protonation of this neutral vinylidene-bridged species (R = H) at -40 degrees C yields an ethylidyne-bridged product which rearranges to a vinylidene- and hydride-bridged product at ambient temperature. Reaction of [Ir-2(Co)(2)(mu-I)(mu-CC(H)Ph)(dppm)(2)][SO3CF3] with either acetylene or phenylacetylene yields alkyne- and phenylvinylidene-bridged products [Ir2I(CO)(2)(mu-CC(H)Ph)(mu-HCCR)(dppm)(2)][SO3CF3] (R = H, Ph), and the X-ray structure of a derivative, [Ir2I2(CO)(2)(mu-CC(H)Ph)(mu-HCCH)(dppm)2] (15), has been carried out. The reaction of [Ir-2(CO)(2)(mu-I)(mu-CCH2)(dppm)(2)][SO3CF3] with phenylacetylene yields an unusual bis(vinylidene) product, [Ir2I(CO)2(CCH2)(CC(H)Ph)(dppm)(2)][SO3CF3] (19), in which each vinylidene is terminally bound to a different metal. Reaction of 19 with either I- or CO converts the terminal vinylidenes to bridging groups yielding [Ir2I(L)(CO)(2)(mu-CCH2)(mu-CC(H)Ph)(dppm)(2)](n+) (L = I, n = 0; L = CO, n = 1). The structure of the diiodo species (20b) has been determined by X-ray techniques. Compound 15, as the CH2Cl2 solvate, crystallizes in the monoclinic space group P2(1)/c with a = 15.799(3) Angstrom, b = 18.029(2) Angstrom, c = 21.126(5) Angstrom, beta = 99.48(2)degrees, V = 5935(4) Angstrom(3) (T = -65 degrees C), and Z = 4. On the basis of 7406 unique observations and 441 parameters varied, the structure refined to R = 0.034 and R(w) = 0.040. This complex has a bridging phenylvinylidene and a bridging acetylene group with the iodo ligands bound cis to the alkyne bridge. Compound 20b crystallizes in the tetragonal space group I4(1)/a with a = 30.407(5) Angstrom, c = 13.065(6) Angstrom, V = 12079(6) Angstrom(3), and Z = 8 (T = 22 degrees C). On the basis of 3730 unique observations and 305 parameters varied, the structure refined to R = 0.045 and R(w) = 0.050. In this product both the vinylidene and the phenylvinylidene groups are bridging, with the iodo ligands having an anti arrangement on adjacent metals.

  DOI：

  10.1021/om00006a054