Suppr超能文献

作为桥连双氮杂环卡宾混合金属配合物前体的碳烯锚定/悬垂咪唑鎓物种。

Carbene-anchored/pendent-imidazolium species as precursors to di-N-heterocyclic carbene-bridged mixed-metal complexes.

机构信息

Department of Chemistry, University of Alberta, Edmonton, Alberta, CanadaT6G 2G2.

出版信息

Dalton Trans. 2009 Sep 21(35):7269-87. doi: 10.1039/b906884h. Epub 2009 Aug 4.

Abstract

Reaction of a series of linked diimidazolium dibromide salts with one-half equivalent of Rh(mu-OAc)(COD) under reflux conditions generates a series of carbene-anchored/pendent-imidazolium complexes, [RhBr(COD)((R)C(H)-eta(1)-C(eth))][Br] ((Me)C(H)-eta(1)-C(eth) = ethylene[(N-methyl)imidazolium][(N-methyl)imidazole-2-ylidene] and (tBu)C(H)-eta(1)-C(eth) = ethylene[(N-tert-butyl)imidazolium][(N-tert-butyl)imidazole-2-ylidene]) via deprotonation of one end of the diimidazolium salt and coordination of the resulting carbene to Rh. Reaction of these complexes with carbon monoxide or the appropriate diphosphine yields either [RhBr(CO)(2)((R)C(H)-eta(1)-C(eth))][Br] (R = Me, (t)Bu) or [RhBr(P( intersection)P)((Me)C(H)-eta(1)-C(eth))][Br] (P( intersection)P = Ph(2)PCH(2)PPh(2), Ph(2)PCH(2)CH(2)PPh(2), Et(2)PCH(2)PEt(2)), respectively. The resulting diphosphine complexes readily decompose in solution. A series of palladium complexes [PdI(3-n)(PR(3))(n)(L)]I (n = 1,2) and [PdI(P( intersection)P)(L)]I (L = (tBu)C(H)-eta(1)-C(meth), (tBu)C(H)-eta(1)-C(eth); (tBu)C(H)-eta(1)-C(meth) = methylene[(N-tert-butyl)imidazolium][(N-tert-butyl)imidazole-2-ylidene]), containing the linked NHC-imidazolium moiety, have also been prepared by reacting the triiodo complexes, [PdI(3)((tBu)C(H)-eta(1)-C(meth))] and [PdI(3)((tBu)C(H)-eta(1)-C(eth))] with several mono- and diphosphines. Attempts to generate mixed Rh/Pd complexes using Pd(OAc)(2) to deprotonate the pendent arm of several of the above carbene-anchored/pendent-imidazolium complexes of Rh have proven unsuccessful. However, a targeted di-NHC-bridged heterobimetallic complex [PdI(2)(PEt(3))(mu-(tBu)CC(meth))RhI(COD)] ((tBu) CC(meth) = 1,1'-methylene-3,3'-di-tert-butyldiimidazol-2,2'-diylidene) can be generated by deprotonation of the imidazolium group in [PdI(2)(PEt(3))((tBu)C(H)-eta(1)-C(meth))][I] using half an equivalent of Rh(mu-OAc)(COD). The X-ray structure determination of this Pd/Rh complex confirms the dicarbene-bridged formulation and shows a metal-metal separation of approximately 6.2 A. Reaction of this Rh/Pd complex with CO yields the corresponding dicarbonyl product [PdI(2)(PEt(3))(mu-(tBu)CC(meth))RhI(CO)(2)] via replacement of the COD ligand. The related dicarbene-bridged Ir/Rh complex [IrBr(COD)(mu-(tBu)CC(meth))RhBr(COD)] can be generated by reaction of [IrBr(COD)((tBu)C(H)-eta(1)-C(meth) )][Br] with Rh(mu-OAc)(COD), while the Pd/Ir complexes [PdI(2)(PR(3))(mu-(tBu)CC(meth))IrI(COD)] (PR(3) = PPh(3), PMe(2)Ph) can be generated by reaction of the monometallic [PdI(2)(PR(3))((tBu)C(H)-eta(1)-C(meth))][I] species with K[N(SiMe(3))(2)] in the presence of Ir(mu-Cl)(COD). The carbonyl analogues, [PdI(2)(PR(3))(mu-(tBu)CC(meth))IrI(CO)(2)], can be generated via a gentle purge of CO gas. These di-NHC-bridged heterobimetallic species represent some of the first examples of this class and are the first involving palladium.

摘要

一系列连接的二咪唑二溴盐与[Rh(mu-OAc)(COD)] 2 的一半当量在回流条件下反应,生成一系列碳烯锚定/悬垂咪唑鎓配合物,[RhBr(COD)((R)C(H)-eta(1)-C(eth))][Br] ((Me)C(H)-eta(1)-C(eth) = 乙烯[(N-甲基)咪唑鎓][(N-甲基)咪唑-2-亚基]和(tBu)C(H)-eta(1)-C(eth) = 乙烯[(N-叔丁基)咪唑鎓][(N-叔丁基)咪唑-2-亚基])通过二咪唑盐的一端去质子化和生成的碳烯与 Rh 的配位。这些配合物与一氧化碳或适当的二膦反应,分别生成[RhBr(CO)(2)((R)C(H)-eta(1)-C(eth))][Br] (R = Me, (t)Bu) 或 [RhBr(P( intersection)P)((Me)C(H)-eta(1)-C(eth))][Br] (P( intersection)P = Ph(2)PCH(2)PPh(2), Ph(2)PCH(2)CH(2)PPh(2), Et(2)PCH(2)PEt(2))。所得的二膦配合物在溶液中容易分解。一系列钯配合物[PdI(3-n)(PR(3))(n)(L)]I (n = 1,2) 和 [PdI(P( intersection)P)(L)]I (L = (tBu)C(H)-eta(1)-C(meth), (tBu)C(H)-eta(1)-C(eth); (tBu)C(H)-eta(1)-C(meth) = 亚甲基[(N-叔丁基)咪唑鎓][(N-叔丁基)咪唑-2-亚基]),含有连接的 NHC-咪唑鎓部分,也通过反应三碘配合物[PdI(3)((tBu)C(H)-eta(1)-C(meth))] 和 [PdI(3)((tBu)C(H)-eta(1)-C(eth))] 与几种单膦和二膦制备。尝试使用 Pd(OAc)(2) 去质子化 Rh 上的几个碳烯锚定/悬垂咪唑鎓配合物的悬垂臂,生成混合的 Rh/Pd 配合物,但证明不成功。然而,通过用一半当量的Rh(mu-OAc)(COD) 去质子化[PdI(2)(PEt(3))((tBu)C(H)-eta(1)-C(meth))][I] ,可以生成目标二-NHC 桥接的杂双金属配合物[PdI(2)(PEt(3))(mu-(tBu)CC(meth))RhI(COD)] ((tBu) CC(meth) = 1,1'-亚甲基-3,3'-二-叔丁基二咪唑-2,2'-二亚基)。该 Pd/Rh 配合物的 X 射线结构测定证实了双二碳烯桥接的结构,并显示出约 6.2 Å 的金属-金属分离。该 Rh/Pd 配合物与 CO 反应生成相应的二羰基产物[PdI(2)(PEt(3))(mu-(tBu)CC(meth))RhI(CO)(2)],通过取代 COD 配体。相关的二碳烯桥接 Ir/Rh 配合物[IrBr(COD)(mu-(tBu)CC(meth))RhBr(COD)] 可以通过反应[IrBr(COD)((tBu)C(H)-eta(1)-C(meth) )][Br] 与Rh(mu-OAc)(COD) 生成,而 Pd/Ir 配合物[PdI(2)(PR(3))(mu-(tBu)CC(meth))IrI(COD)] (PR(3) = PPh(3), PMe(2)Ph) 可以通过反应生成在Ir(mu-Cl)(COD) 的存在下,将单金属[PdI(2)(PR(3))((tBu)C(H)-eta(1)-C(meth))][I] 物种与 K[N(SiMe(3))(2)] 反应。通过轻轻吹扫 CO 气体可以生成羰基类似物[PdI(2)(PR(3))(mu-(tBu)CC(meth))IrI(CO)(2)]。这些二-NHC 桥接的杂双金属物种代表了这一类的一些首批实例,并且是第一个涉及钯的实例。

文献AI研究员

20分钟写一篇综述,助力文献阅读效率提升50倍。

立即体验

用中文搜PubMed

大模型驱动的PubMed中文搜索引擎

马上搜索

文档翻译

学术文献翻译模型,支持多种主流文档格式。

立即体验