Bartolomé Camino, Ramiro Zoraida, Pérez-Galán Patricia, Bour Christophe, Raducan Mihai, Echavarren Antonio M, Espinet Pablo
IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, UniVersidad de Valladolid, E-47071 Valladolid, Spain.
Inorg Chem. 2008 Dec 1;47(23):11391-7. doi: 10.1021/ic801446v.
Complexes [AuCl{C(NHR)(NHPy-2)}] (Py-2 ) 2-pyridyl; R ) Me, tBu, nBu, iPr, nheptyl) have been prepared in amodular way from [AuCl(CNPy-2)]. The carbene moiety has a hydrogen-bond supported heterocyclic structure similar to the nitrogen heterocyclic carbenes in the solid state, and in CH2Cl2 or acetone solution, which is open in the presence of MeOH. The compounds are good catalysts for the skeletal rearrangement of enynes, and for the methoxycyclization of enynes. In contrast, the complexes [AuCl{C(NHR)(NHPy-4)}] are scarcely active due to the blocking effect of the coordination position required for the catalysis by the nitrogen of the NHPy-4 group.
配合物[AuCl{C(NHR)(NHPy - 2)}]（Py - 2为2 - 吡啶基；R = 甲基、叔丁基、正丁基、异丙基、正庚基）已通过[AuCl(CNPy - 2)]以模块化方式制备。卡宾部分具有氢键支持的杂环结构，在固态以及二氯甲烷或丙酮溶液中类似于氮杂环卡宾，在甲醇存在下该结构是开放的。这些化合物是烯炔骨架重排以及烯炔甲氧基环化的良好催化剂。相比之下，配合物[AuCl{C(NHR)(NHPy - 4)}]由于NHPy - 4基团的氮对催化所需配位位置的阻断作用而几乎没有活性。
