Canepa Giuseppe, Brandt Carsten D, Ilg Kerstin, Wolf Justin, Werner Helmut
Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Chemistry. 2003 Jun 6;9(11):2502-15. doi: 10.1002/chem.200204623.
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.
[[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。
