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美国卫生研究院文献>Acta Crystallographica Section E: Crystallographic Communications
>Syntheses and crystal structures of IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}ClHCl·2.75CH2Cl2 and its derivatives IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}(CH2CO2Et)ClCl·CH3OH·0.5H2O IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}Cl2Cl·CH3OH·2H2O and IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}(CH2CO2Et)(CO)Cl2·2CH2Cl2·1.5H2O
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Syntheses and crystal structures of IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}ClHCl·2.75CH2Cl2 and its derivatives IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}(CH2CO2Et)ClCl·CH3OH·0.5H2O IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}Cl2Cl·CH3OH·2H2O and IrIII{C(CHCO2Et)(dppm)2-κ4PCC′P′}(CH2CO2Et)(CO)Cl2·2CH2Cl2·1.5H2O
The common feature of the four iridium(III) salt complexes, (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4 P,C,C′,P′)chloridohydridoiridium(III) chloride methylene chloride 2.75-solvate (>4), (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4 P,C,C′,P′)chlorido(ethoxyoxoethanido)iridium(III) chloride–methanol–water (1/1/0.5) (>5), (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4 P,C,C′,P′)dichloridoiridium(III) chloride–methanol–water (1/1/2) (>6) and (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4 P,C,C′,P′)carbonyl(ethoxyoxoethanide)iridium(III) dichloride–methylene chloride–water (1/2/1.5) >(7) or in terms of their formulae [Ir(C55H50O2P4)ClH]Cl·2.75CH2Cl2 (>4), [Ir(C4H7O2)(C55H50O2P4)Cl]Cl·CH3OH·0.5H2O (>5), [Ir(C55H50O2P4)Cl2]Cl·CH3OH·2H2O (>6) and [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2O (>7) is a central IrIII atom coordinated in a distorted octahedral fashion by a PCCP ligand system and two additional residues, such as chlorides, a hydride, a carbonyl or an alkyl unit. Thereby, the PCP pincer ligand system and the residue trans to the carbodiphosphorane (CDP) C atom surround the iridium(III) transition metal in the equatorial plane under the formation of two five-membered dissimilar chelate rings [C—CCDP—P (>4, >5, >6 and >7) for the first ring: 120.2 (3), 121.9 (5), 111.2 (3) and 121.7 (2) °; for the second ring: 112.1 (3), 113.5 (5), 120.5 (3) and 108.3 (2)°]. A cyclopropane-like heterocycle is positioned approximately orthogonal (84.21–88.85°) to the equatorial plane, including an alkylidene bridge connecting the IrIII atom and the coordinating CDP atom of the PCP subunit. In general, the neutral PCCP ligand system coordinates the metal in a tetradentate way via three Lewis acid/base bonds and by an alkylidene unit presenting strengthened interactions. In all the crystal structures, (disordered) solvent molecules are present in the voids of the packed molecules that interact with the positively charged complex and its chloride counter-ion(s) through weak hydrogen bonding.
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机译:四种铱(III)盐配合物的共同特征是(双{[[((二苯基膦基)甲基]二苯基膦亚基}(乙氧基氧杂亚锡)甲烷-κ 4 sup> P,C,C',P')氯氢化铱( III)氯甲烷2.75-溶剂化物(> 4 strong>),(双{[[((二苯基膦基甲基)甲基]二苯基膦亚基}(乙氧基氧杂亚烷基)甲烷-κ 4 sup> P,C,C' ,P')氯代(乙氧基氧杂蒽基)铱氯化钠-甲醇-水(1/1 / 0.5)(> 5 strong>),(双{[((二苯膦基)甲基]二苯基膦亚基}(乙氧基氧代乙叉基)甲烷-κ 4 sup> P,C,C',P')氯化二氯铱(III)-甲醇-水(1/1/2)(> 6 strong>)和(bis { [[(二苯基膦基)甲基]二苯基膦亚基}(乙氧基氧杂亚烷基)甲烷-κ 4 sup> P,C,C',P')羰基(乙氧基氧杂锡)铱(III)二氯化物-二氯甲烷-水(1/2 /1.5)>(7) strong>或根据它们的公式[Ir(C55H50O2P4)ClH] Cl·2.75CH2Cl2 (> 4 strong>),[Ir(C4H7O2)(C55H50O2P4)Cl] Cl·CH3OH·0.5H2O(> 5 strong>),[Ir(C55H 50 sub> O 2 sub> P 4 sub>)Cl 2 sub>] Cl·CH 3 sub> OH·2H 2 sub > O(> 6 strong>)和[Ir(C 4 sub> H 7 sub> O 2 sub>)(C 55 sub> H 50 sub> O 2 sub> P 4 sub>)(CO)] Cl 2 sub>·2CH 2 sub> Cl 2 sub>·1.5H 2 sub> O(> 7 strong>)是中心配位的Ir III sup>原子通过PCCP配体系统以扭曲的八面体形式和两个另外的残基,例如氯化物,氢化物,羰基或烷基单元。因此,PCP钳形配体系统和碳二磷环(CDP)C原子的 trans em>残基在两个五个五元异螯合物环的形成下围绕着赤道平面中的铱(III)过渡金属[ C—C CDP sub> —P(> 4 strong>,> 5 strong>,> 6 strong>和> 7 strong>)对于第一环:120.2(3),121.9(5),111.2(3)和121.7(2)°;对于第二个环:112.1(3),113.5(5),120.5(3)和108.3(2)°]。类似于环丙烷的杂环与赤道平面近似正交(84.21–88.85°),包括连接Ir III sup>原子和PCP亚基的配位CDP原子的亚烷基桥。通常,中性PCCP配体系统通过三个路易斯酸/碱键和呈现增强相互作用的烷基亚烷基单元,以四齿的方式配位金属。在所有晶体结构中,(无序)溶剂分子存在于填充分子的空隙中,这些分子通过弱氢键与带正电荷的配合物及其氯离子抗衡离子相互作用。
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