IrCl(CH=CHCO2Me)(CCCO2Me)(κ(2)(P,O)-iPr2PCH2CH2OMe)(κ(P)-iPr2PCH2CH2OMe) | 167955-02-4

• 英文名称: IrCl(CH=CHCO2Me)(CCCO2Me)(κ(2)(P,O)-iPr2PCH2CH2OMe)(κ(P)-iPr2PCH2CH2OMe)
• CAS: 167955-02-4
• 化学式: C₂₆H₅₀ClIrO₆P₂
• 分子量: 748.3
• InChiKey: SJSNQAMZRNGHTB-UHFFFAOYSA-M

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：

  IrClH(κ(2)(C,P)-CH2OCH2CH2PiPr2)(κ(2)(P,O)-iPr2PCH2CH2OMe) 、 丙炔酸甲酯 以 苯 为溶剂， 以61%的产率得到IrCl(CH=CHCO2Me)(CCCO2Me)(κ(2)(P,O)-iPr2PCH2CH2OMe)(κ(P)-iPr2PCH2CH2OMe)
  参考文献：
  名称：

  双功能膦配体和底物：从i-Pr2PCH2CH2X（X = OMe，NMe2）合成铱氢，羰基，炔基，乙烯基和亚乙烯基配合物，包括一种不常见的环金属化产物的X射线晶体结构

  摘要：

  Treatment of [IrCl(C8H14)(2)](2) (5) with i-Pr(2)PCH(2)CH(2)OMe (6) leads to the formation of the octahedral hydridoiridium(III) complex [IrHCl{kappa(2)(C,P)-CH(2)OCH(2)CH(2)Pi-Pr-2} {kappa(2)(P,O)-i-Pr-2-PCH(2)CH(2)OMe}] (8), which according to the X-ray structure analysis contains both a five- and a six-membered chelate ring. In contrast to 6, the phosphinoamine i-Pr(2)PCH(2)CH(2)NMe(2) (7) reacts with 5 to give the expected square-planar iridium(I) compound trans-[IrCl{kappa(P)-i-Pr(2)PCH(2)CH(2)NMe(2)}{kappa(2)(P,N)-i-Pr(2)PCH(2)CH(2)NMe(2)}] (9), which in solution at room temperature is nonfluxional on the NMR time scale. Reaction of 9 with CO yields four-coordinate trans-[IrCl(CO){kappa(P)-i-Pr(2)PCH(2)CH(2)NMe(2)}(2)] (10), while on treatment of 9 with HCl in benzene the six-coordinate [IrHCl2{kappa(P)-i-Pr(2)PCH(2)CH(2)NMe(2)}{kappa(2)(P,N)-i-Pr(2)PCH(2)CH(2)NMe(2)}] (11) is obtained. Compound 11 is also one of the products of the reaction of 9 with CH2Cl2 which equally gives small quantities of the ionic bis(chelate) complex [IrCl2{kappa(2)(C,P)-CH(2)NMe(2)CH(2)CH(2)Pi-Pr-2}{kappa(2)(P,N)-i-Pr(2)PCH(2)CH(2)NMe(2)}]Cl (12). The chlorodihydrido and dichlorohydrido complexes [IrH(Cl)X{kappa(P)-i-Pr(2)PCH(2)CH(2)OMe}{kappa(2)(P,O)-i-Pr(2)PCH(2)CH(2)OMe}] (13, X = H; 14, X = Cl) are formed at room temperature almost instantaneously from 8 and H-2 or HCl, respectively. At 80 degrees C, the reaction of 8 (or 13) with methyl acrylate and methyl vinyl ketone affords the hydrido(vinyl)iridium(III) derivatives [IrHCl{kappa(2)(C,O)-CH=CHC(R)=O}{kappa(P)-i-Pr(2)PCH(2)CH(2)OMe}(2)] (15, R = OMe; 16, R = Me), whereas with HC=CR the alkynyl(hydrido) compounds [IrH(C=CR)Cl{kappa(P)-i-Pr(2)PCH(2)CH(2)OMe}{kappa(2)(P,O)-i-Pr(2)PCH(2)CH(2)OMe}] (17, R = Ph; 18, R = CO(2)Me) are obtained. Thermal or photochemical rearrangement of 17 and 18 leads to the formation of the isomeric vinylideneiridium(I) complexes trans-[IrCl(=C=CHR)-{kappa(P)-i-Pr(2)PCH(2)CH(2)OMe}(2)] (20,21) in good yield. The octahedral alkynyl(vinyl) compound [IrCl(C=CCO(2)Me)(CH=CHCO(2)Me){kappa(P)-i-Pr(2)PCH(2)CH(2)OMe}{kappa(2)(P,O)-i-Pr2PCH2CH2-OMe}] has been prepared from either 8 or 13 and excess HC=CCO(2)Me. Chloride abstraction of 20 and 21 with AgSbF6 affords the SbF6 salts of the cationic complexes [Ir(=C=CHR){kappa(P)-i-Pr(2)PCH(2)CH(2)OMe}{kappa(2)(P,O)-i-Pr(2)PCH(2)CH(2)OMe}](+) (22, 23), in which according to the X-ray structure analysis of 23 the vinylidene ligand and the methoxy unit are trans disposed.

  DOI：

  10.1021/om00008a013