Synthesis, Molecular Structure, and Reactivity of Iridium(I) and Iridium(III) Complexes Formed by Coordination and C−H Activation of the Substituted Arenes C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>CH<sub>2</sub>P<i>i</i>Pr<sub>2</sub> and C<sub>6</sub>H<sub>5</sub>OCH<sub>2</sub>CH<sub>2</sub>P<i>t</i>Bu<sub>2</sub>
作者:Giuseppe Canepa、Eduardo Sola、Marta Martín、Fernando J. Lahoz、Luis A. Oro、Helmut Werner
DOI:10.1021/om0210457
日期:2003.5.1
and 11 with acetonitrile lead to the cleavage of the arene−metal bond and afford the octahedral iridium(III) complexes [IrH2(NCCH3)3(L1-κ-P)]BF4 (15) and [IrH(C6H4CH2CH2PiPr2-κ2-C,P)(NCCH3)3]BF4 (16), respectively. Treatment of the C−H activation product 16 with H2 yields 15. The X-ray crystal structure analysis of 16 reveals that the Ir(NCCH3)3 fragment possesses the fac configuration.
二聚体[Ir(μ-Cl)(C 8 H 14)2 ] 2(1)与AgPF 6在丙酮中反应,生成双(丙酮)加合物顺式-[Ir(丙酮)2(C 8 H 14)2 ] PF 6(2),其在治疗与我镨2 PCH 2 CH 2 C ^ 6 ħ 5(L 1),得到半夹心型配合物[(η 6 -L 1 - κ -P)Ir(C 8 H 14)] PF 6(3)。甲氧基桥接的二聚体[Ir(μ-OMe)(C 8 H 12)] 2(4)经磷鎓盐L 1 ·HBF 4处理后得到化合物[Ir(C 8 H 12)(丙酮)(L 1 - κ - P)] BF 4(5),而使用L 2 ·HBF 4(L 2 = t Bu 2 PCH 2 CH 2OC 6 H ^ 5)双(螯合物)配合物[Ir(C 8 H ^ 12)(L 2 - κ 2 - O,P)] BF 4(6)被产生。两个5和6与氢反应的丙酮,得到dihydridoiridium(III)的衍生物[(η
Half-Sandwich Type Rhodium(I) Complexes with Arenes and Functionalized Arenes C<sub>6</sub>H<sub>5</sub>X(CH<sub>2</sub>)<i><sub>n</sub></i>PR<sub>2</sub> (R = <i>i</i>Pr, <i>t</i>Bu) as Nonchelating and Chelating Ligands
作者:Helmut Werner、Giuseppe Canepa、Kerstin Ilg、Justin Wolf
DOI:10.1021/om0004646
日期:2000.11.1
(10) with the new alkyldiisopropylphosphines iPr2P(CH2)nC6H5 (8, n = 2; 9, n = 3), which were prepared from HPiPr2 and C6H5(CH2)nBr in the presence of ammonia, in the molar ratio of 1:1 gave the half-sandwich type complexes [η6-C6H5(CH2)nPiPr2-κ-P}Rh(C8H14)]PF6 (11, 12). They afforded upon treatment with a second equivalent of 8 or 9 the bis(phosphine) compounds [η6-C6H5(CH2)nPiPr2-κ-P}C6H5(CH2)nPiPr2-κ-P}Rh]PF6
一系列arenerhodium的(I)配合物[(η 6 -arene)的Rh(C 8 H ^ 14)(P我镨3)] PF 6(2 - 6)从高反应性的起始原料,制备顺式- [铑(C 8 H 14)(P i Pr 3)(丙酮)2 ] PF 6(1)和芳烃在CH 2 Cl 2中的产率极高。相关乙烯化合物[(η 6 -C 6 H ^ 6)的Rh(C 2 H ^通过在乙烯气氛下搅拌相应的环辛烯衍生物2的溶液,得到4)(P i Pr 3)] PF 6(7)。的反应顺- [铑(C 8 H ^ 14)2(丙酮)2 ] PF 6(10)与新的alkyldiisopropylphosphines我镨2 P(CH 2)Ñ ç 6 ħ 5(8,Ñ = 2; 9,Ñ= 3),这是从HP制备我镨2和C 6 H ^ 5(CH 2)ñ溴在氨的存在下,在1:1摩尔比,得到半夹心型配合物[η 6 -C 6 ħ 5(CH 2)ñ