EaStCHEM, School of Chemistry, Purdie Building, University of St. Andrews, St. Andrews, Fife Scotland KY16 9ST, UK.
Dalton Trans. 2014 Mar 7;43(9):3479-91. doi: 10.1039/c3dt52552j.
The coordination chemistry and solution behaviour of Rh(i) and Ru(ii) complexes derived from mixed anhydride ligands of carboxylic acids and phosphorus acids were explored. Similar to the free ligand systems, mixed anhydride complexes rearranged in solution via a number of pathways, with the pathway of choice dependent on the mixed anhydride employed, the auxiliary ligands present as well as the nature of the metal centre. Plausible mechanisms for some of the routes of rearrangement and by-product formation are proposed. Where stability allowed, new complexes were fully characterised, including solid state structures for four of the unrearranged mixed anhydride complexes and two of the interesting rearrangement products.
探索了羧酸和磷酸混合酸酐配体衍生的 Rh(i)和 Ru(ii)配合物的配位化学和溶液行为。与游离配体体系相似,混合酸酐配合物在溶液中通过多种途径重排,选择的途径取决于所使用的混合酸酐、存在的辅助配体以及金属中心的性质。对一些重排和副产物形成途径提出了合理的机制。在允许稳定的情况下,对新的配合物进行了充分的表征,包括四个未重排的混合酸酐配合物和两个有趣的重排产物的固态结构。