[((η5-C5Me5)Ir)3(μ3-S)2] | 156342-66-4

• 英文名称: [((η5-C5Me5)Ir)3(μ3-S)2]
• CAS: 156342-66-4
• 化学式: C₃₀H₄₅Ir₃S₂
• 分子量: 1046.48
• InChiKey: STLHDXGPYRFEFW-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：

  双(环戊二烯)钴 、 [((η5-C5Me5)Ir)4(μ3-S)2(μ-H)2][BF4]2*0.5CH2Cl2 以 乙腈 为溶剂， 以36%的产率得到[((η5-C5Me5)Ir)3(μ3-S)2]
  参考文献：
  名称：

  Properties and Reactivities of the Hydrido Ligands in Iridium Sulfido Clusters Relevant to Activation and Production of H₂

  摘要：

  Sulfido-hydrido clusters whose cores consist of three to six iridium atoms, [(Cp*Ir)(3)(mu(3)-S)(mu(2)-H)(3)][BF4] (2), [(Cp*Ir)(4)(mu(3)-S)(2)(mu(2)-H)(3)][BF4] (3), [(Cp*IrH)(2)(CP*Ir)(mu(3)-S)(mu(2)-H)(2)], [(Cl)*IrH)(4)(mu(4)-S)(mu(2)-H)(2)], and [(Cp*Ir)(5)Ir(mu(3)-S)(5)H], were isolated from the reactions of [(Cp*Ir)(2)(mu(2)-H)(3)][BF4] (CP* = eta(5)-C5Me5) with NaSH in MeOH. Treatment of 2 with KOBut afforded the deprotonated product [(Cp*Ir)(3)(mu(3)-S)(mu-H)(2)] (7), which was protonated by HBF4 to give 2 reversibly. Addition of HBF4 to 3 formed the dicationic cluster [(Cp*Ir)(4)(mu(3)-S)(2)(mu-H)(2)][BF4](2) (10) with concurrent evolution of H-2, which was converted back to 3 under H-2 atmosphere in the presence of excess pyridine at 50 degrees C. In contrast, reactions of 10 with H-2 conducted in the presence of various alkylamines at 20-50 degrees C afforded the mixtures of 3 and its stereoisomer 11. Conversion of 10 into 3 was also achieved by the reaction with 2 equiv Of Cp2CO in the presence of [Et3NH][BF4], which furnished the cycle of reducing H+- into H-2 mediated by the Ir4S2 cluster. Cluster 10 readily reacted with CO (1 atm) at 20 degrees C to give [(Cp*Ir)(4)(mu(3)-S)(2)(mu-H)(2)(CO)][BF4](2) (13), where the CO ligand was bound in an end-on fashion to one of the two Ir centers connected to two mu(3)-sulfido ligands. Analogous adduct formation was observed in the reaction of 10 with I equiv of XyNC (Xy = 2,6-dimethylphenyl), yielding two stereoisomers of [(Cp*Ir)(4)(mu(3)-S)(2)(mu-H)(2)(CNXy)][BF4](2), one of which was the analogue of 13 and the other had the XyNC ligand coordinating to the same Ir site but with the inverted orientation around the metal. On the other hand, treatment of 10 with excess N2H4 gave the hydrazine cluster [(Cp*Ir)(4)(mu(3)-S)(2)(mu(2)-H)(2)(N2H4)(2)][BF4](2), in which two terminal hydrazine ligands were bonded to one of two Ir sites supported by only one mu(3-)sullfido ligand. On the basis of these findings about the adduct formations, reaction pathways of 10 with H-2 in the presence of bases are discussed. Structures of all new clusters reported here were determined by spectroscopic methods and, except for 7, by X-ray crystallography.

  DOI：

  10.1021/om701207j