Structure and Dynamics of Imidazolium- and Pyridinium-Substituted 畏3-Cycloheptatrienide-Pd Complexes
详细信息 查看全文
- 作者：Christian Jandl ; Karl 脰fele ; Fritz E. K眉hn ; Wolfgang A. Herrmann ; Alexander P枚thig
- 刊名：Organometallics
- 出版年：2014
- 出版时间：November 24, 2014
- 年：2014
- 卷：33
- 期：22
- 页码：6398-6407
- 全文大小：488K
- ISSN：1520-6041
文摘
A range of imidazolium- and pyridinium-substituted 畏3-cycloheptatrienide-Pd complexes was synthesized by nucleophilic attack of different N-donors on cycloheptatrienylidene-Pd complexes. Their full characterization is reported along with DFT studies of their formation and special properties. The target compounds represent the first crystallographically characterized monomeric allyl complexes of a Pd dihalide. The cationic substituents on the cycloheptatrienide ring form strong intramolecular H-bonds to one bromide ligand. The Pd鈥揳llyl bond was found to be highly fluxional, showing a continuous migration of the metal along the seven-membered ring even at low temperatures. The exchange of one bromide for a weakly coordinating anion yields dimeric structures and improves the poor solubility of these complexes, allowing their further synthetic utilization.