[RhIr(CC(C6H5))(CO)(CN(n-C4H9))2(μ-S)2((C6H5)2PCH2P(C6H5)2)2][BF4] | 286847-74-3

• 英文名称: [RhIr(CC(C6H5))(CO)(CN(n-C4H9))2(μ-S)2((C6H5)2PCH2P(C6H5)2)2][BF4]
• CAS: 286847-74-3
• 化学式: BF₄*C₆₉H₆₇IrN₂OP₄RhS₂
• 分子量: 1510.26
• InChiKey: YEPQTEFGXPJKOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  [RhIr(CO)2(μ2-η1:η2-C2(C6H5))((C6H5)2PCH2P(C6H5)2)2][BF4] 、 丁基异硫氰酸酯 以 四氢呋喃 为溶剂， 生成 [RhIr(CC(C6H5))(CO)(CN(n-C4H9))2(μ-S)2((C6H5)2PCH2P(C6H5)2)2][BF4]
  参考文献：
  名称：

  Sulfur–carbon bond formation and bond cleavage in alkynyl-bridged heterobinuclear complexes of rhodium and iridium

  摘要：

  The phenylacetylide-bridged heterobinuclear complexes [RhIr(CO)(2)(mu-eta(1):eta(2)-C2Ph)(dppm)(2)][X] (X = BF4, SO3CF3; dppm = Ph2PCH2PPh2) (1) react with carbon disulfide to give several products. At temperatures between - 60 and - 80 degrees C the first product, [RhIr(CO)(eta(2)-CS2)(mu-CO)(mu-eta(1):eta(2)-C2Ph)(dppm)(2)][X] (2), is the result of CS2 coordination at Ir. Upon warming, two products are formed as a result of condensation of two CS2 groups. In [RhIr(CO)(mu-eta(1):eta(3)-CC(Ph)SCSCS2)(mu-CO)(dppm)(2)][X] (3); the resulting C2S4 fragment has also condensed at the beta-carbon of the acetylide group to give a heteroatom-substituted vinylidene group. The other identified product, [RhIr(CO)(C2S4)(mu-C2Ph)(mu-CO)(dppm)(2)][X] (4), is very similar to 3 apart from the absence of coupling of the C2S4 moiety and the acetylide group. Compound 3 appears to be formed independently of 4, but also slowly transforms into 4 by cleavage of a C-S bond. The reaction of 1 with (BuNCS)-Bu-n at - 80 degrees C yields [RhIr(CO)(eta(2) -(SCNBu)-Bu-n)(mu-CCPh)(mu-Co)(dppm)(2)][X] (5), analogous to 2, and upon warming this rearranges to the isothiocyanate-bridged product [RhIr(CCPh)(CO)(2)(mu-(SCNBu)-Bu-n)(dppm)(2)][X] (6). Compound 6 undergoes S-C bond cleavage to yield [RhIr(CCPh)(CO)((CNBu)-Bu-n)(mu-S)(mu-CO)(dppm)(2)][X] (7), slowly at ambient temperature or within hours under reflux. Although no simple adducts analogous to 5 and 6 were observed with (BuNCS)-Bu-t, refluxing 1 in the presence of an excess of this substrate yields [RhIr(CCPh)(CO)((CNBu)-Bu-t)(mu-S),(mu-CO)(dppm)(2)][X] (9) as the major product along with smaller amounts of [RhIr(CCPh)(CO)((CNBu)-Bu-t)(mu-S)(mu-CO)(dppm)(2)][X] (8), analogous to compound 7, Refluxing 1 in the presence of excess (BuNCS)-Bu-n also yields some of the bis-n-butylisocyanide product, analogous to 9. The X-ray structures of compounds 3 (SO3CF3- salt), 7 (BF4- salt) and 9(BF4- salt) are reported. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00605-2