[RhIr(CO)2(μ2-η1:η2-C2(C6H5))((C6H5)2PCH2P(C6H5)2)2][BF4] | 255826-90-5

• 英文名称: [RhIr(CO)2(μ2-η1:η2-C2(C6H5))((C6H5)2PCH2P(C6H5)2)2][BF4]
• CAS: 255826-90-5
• 化学式: BF₄*C₆₀H₄₉IrO₂P₄Rh
• 分子量: 1307.87
• InChiKey: GLDLDHQHOXEKGV-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

• 作为反应物：
  描述：

  [RhIr(CO)2(μ2-η1:η2-C2(C6H5))((C6H5)2PCH2P(C6H5)2)2][BF4] 、 3-溴丙烯 以 二氯甲烷 为溶剂， 以72%的产率得到[RhIrBr(CO)(μ-CCPhCH2CH=CH2)(μ-CO)(dppm)2]BF4
  参考文献：
  名称：

  铑和铱的苯乙炔桥连杂双核络合物中烯丙基到炔基迁移的不寻常例子

  摘要：

  所述的反应性炔基-桥连的络合物[RhIr（CO）2（μ 2 -η 1：η 2 -C 2 PH）（DPPM）2 ] [X]（X = BF 4（1A），SO 3 CF 3（1b）; dppm = Ph 2 PCH 2 PPh 2）与亲电试剂已被证明。质子酸HX（X = BF 4，SO 3 CF 3）第一，得到氧化加成产物[RhIr（X）（CO）2（μ-H）（μ-C 2 PH）（DPPM）2] [X]，这下一氧化碳结果在弱配位BF的位移4 -或SO 3 CF 3 -的阴离子和随后转化为亚乙烯基桥连[RhIr（CO）4（μ-CC（H）的pH）（ dppm）2 ] [X] 2。的反应1与烯丙基卤化物产生的烯丙基亚乙烯基桥连的化合物[RhIr（Y）（CO）（μ-CC（PH）CH 2 CH CH 2）（μ-CO）（DPPM）2 ] [X]（Y =溴（5），氯（6）），通过在炔基部分的β位置偶联炔基和烯丙

  DOI：

  10.1021/om9906565
• 作为产物：
  描述：

  [RhIr(CO)(η2-CS2)(μ-CO)(μ-η1:η2-CC(C6H5))((C6H5)2PCH2P(C6H5))2][BF4] 生成 [RhIr(CO)2(μ2-η1:η2-C2(C6H5))((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