由庞大的官能化膦通过配位和C-H活化形成的铑（I）和铑（III）配合物。

Rhodium(I) and rhodium(III) complexes formed by coordination and C-H activation of bulky functionalized phosphanes.

作者信息

Canepa Giuseppe, Brandt Carsten D, Ilg Kerstin, Wolf Justin, Werner Helmut

机构信息

Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.

出版信息

Chemistry. 2003 Jun 6;9(11):2502-15. doi: 10.1002/chem.200204623.

DOI:10.1002/chem.200204623

PMID:12794893

Abstract

The reaction of [RhCl(C(8)H(14))(2)] (2) with iPr(2)PCH(2)CH(2)C(6)H(5) (L(1)) led, via the isolated dimer [RhCl(C(8)H(14))(L(1))] (3), to a mixture of three products 4 a-c, of which the dinuclear complex [RhCl(L(1))(2)] (4 a) was characterized by Xray crystallography. The mixture of 4a-c reacts with CO, ethene, and phenylacetylene to give the square-planar compounds trans-[RhCl(L)(L(1))(2)] (L=CO (5), C(2)H(4) (6), C=CHPh (9)). The corresponding allenylidene(chloro) complex trans-[RhCl(=C=C=CPh(2))(L(1))(2)] (11), obtained from 4 a-c and HC triple bond CC(OH)Ph(2) via trans-[RhCl=C=CHC(OH)Ph(2)(2)] (10), could be converted stepwise to the related hydroxo, cationic aqua, and cationic acetone derivatives 12-14, respectively. Treatment of 2 and [RhCl(C(2)H(4))(2)] (7) with two equivalents of tBu(2)PCH(2)CH(2)C(6)H(5) (L(2)) gave the dimers [RhCl(C(8)H(14))(L(2))] (15) and [RhCl(C(2)H(4))(L(2))] (16), which both react with L(2) in the molar ratio of 1:2 to afford the five-coordinate aryl(hydrido)rhodium(III) complex [RhHCl(C(6)H(4)CH(2)CH(2)PtBu(2)-kappa(2)C,P)(L(2))] (17) by C-H activation. The course of the reactions of 17 with CO, H(2), PhC triple bond CH, HCl, and AgPF(6), leading to the compounds 19-21, 24, and 25 a, respectively, indicate that the coordinatively unsaturated isomer of 17 with the supposed composition [RhCl(L(2))(2)] is the reactive species. Labeling experiments using D(2), DCl, and PhC triple bond CD support this proposal. With either [Rh(C(8)H(14))(eta(6)-L(2)-kappaP]PF(6) or [Rh(C(2)H(4))(eta(6)-L(n)-kappaP]PF(6) (n=1 and 2) as the starting materials, the corresponding halfsandwich-type complexes 27, 28, and 32 were obtained. The nonchelating counterpart of the dihydrido compound 32 with the composition [RhH(2)(PiPr(3))(eta(6)-C(6)H(6))]PF(6) (35) was prepared stepwise from [Rh(C(2)H(4))(PiPr(3))(eta(6)-C(6)H(6))]PF(6) and H(2) in acetone via the tris(solvato) species [RhH(2)(PiPr(3))(acetone)(3)]PF(6) (34) as intermediate. The synthesis of the bis(chelate) complex [Rh(eta(4)-C(8)H(12))(C(6)H(5)OCH(2)CH(2)PtBu(2)-kappa(2)O,P)]BF(4) (39) is also described. Besides 4 a, the compounds 17, 25 a, and 39 have been characterized by Xray crystal structure analysis.

摘要

[[RhCl(C₈H₁₄)₂]₂] (2) 与 iPr₂PCH₂CH₂C₆H₅ (L₁) 反应，通过分离得到的二聚体 [[RhCl(C₈H₁₄)(L₁)]₂] (3)，生成三种产物 4 a - c 的混合物，其中双核配合物 [[RhCl(L₁)₂]₂] (4 a) 通过 X 射线晶体学进行了表征。4 a - c 的混合物与 CO、乙烯和苯乙炔反应，生成平面正方形化合物 trans - [RhCl(L)(L₁)₂] (L = CO (5)、C₂H₄ (6)、C≡CHPh (9))。由 4 a - c 和 HC≡CC(OH)Ph₂ 通过 trans - [RhCl=C=CHC(OH)Ph₂₂] (10) 得到的相应亚丙二烯基（氯）配合物 trans - [RhCl(=C=C=CPh₂)(L₁)₂] (11)，可分别逐步转化为相关的羟基、阳离子水合和阳离子丙酮衍生物 12 - 14。用两当量的 tBu₂PCH₂CH₂C₆H₅ (L₂) 处理 2 和 [[RhCl(C₂H₄)₂]₂] (7)，得到二聚体 [[RhCl(C₈H₁₄)(L₂)]₂] (15) 和 [[RhCl(C₂H₄)(L₂)]₂] (16)，它们都以 1:2 的摩尔比与 L₂ 反应，通过 C - H 活化得到五配位芳基（氢）铑（III）配合物 [RhHCl(C₆H₄CH₂CH₂PtBu₂ - κ²C,P)(L₂)] (17)。17 与 CO、H₂、PhC≡CH、HCl 和 AgPF₆ 反应分别生成化合物 19 - 21、24 和 25 a 的反应过程表明，推测组成为 [RhCl(L₂)₂] 的 17 的配位不饱和异构体是反应活性物种。使用 D₂、DCl 和 PhC≡CD 进行的标记实验支持了这一推测。以 [Rh(C₈H₁₄)(η⁶ - L₂ - κP]PF₆ 或 [Rh(C₂H₄)(η⁶ - Lₙ - κP]PF₆（n = 1 和 2）为起始原料，得到了相应的半夹心型配合物 27、28 和 32。通过 [Rh(C₂H₄)(PiPr₃)(η⁶ - C₆H₆)]PF₆ 和 H₂ 在丙酮中经三（溶剂）物种 [RhH₂(PiPr₃)(丙酮)₃]PF₆ (34) 作为中间体逐步制备了组成为 [RhH₂(PiPr₃)(η⁶ - C₆H₆)]PF₆ (35) 的二氢化物 32 的非螯合类似物。还描述了双（螯合物）配合物 [Rh(η⁴ - C₈H₁₂)(C₆H₅OCH₂CH₂PtBu₂ - κ²O,P)]BF₄ (39) 的合成。除了 4 a 之外，化合物 17、25 a 和 39 已通过 X 射线晶体结构分析进行了表征。