Reinholdt Anders, Bendix Jesper
Department of Chemistry, University of Copenhagen , Universitetsparken 5, 2100 Copenhagen, Denmark.
Inorg Chem. 2017 Oct 16;56(20):12492-12497. doi: 10.1021/acs.inorgchem.7b01956. Epub 2017 Sep 25.
We report the observation of the weakening of the RuC-Pt single bond in (CyP)ClRu≡C-PtCl-L (Ru≡C-Pt-L) complexes, leading to the incipient formation of the terminal ruthenium carbide complex, (CyP)ClRu≡C (RuC). In the solid state, elongation of RuC-Pt bonds illustrates the degree of weakening, and in solution, decreasing platinum-carbide coupling constants and increasing carbide chemical shifts reveal weaker interaction through the carbide bridge, as the electron donating ability of L becomes progressively stronger. For the bridging carbide ligands, the chemical shifts and coupling constants to platinum are linearly dependent, and NMR data for parent RuC conform to this relationship, providing a spectroscopic means of determining the strength of the RuC-Pt linkages relative to dissociated RuC. The pliancy of the Ru≡C-Pt-L fragment with regard to the identity of L establishes the carbide-bridged complexes as remarkably wide-ranging and sensitive probes for ligand donor abilities.
我们报告了在（CyP）ClRu≡C-PtCl-L（Ru≡C-Pt-L）配合物中RuC-Pt单键减弱的观察结果，这导致了末端碳化钌配合物（CyP）ClRu≡C（RuC）的初步形成。在固态中，RuC-Pt键的伸长说明了减弱程度，而在溶液中，随着L的给电子能力逐渐增强，铂-碳化物耦合常数的降低和碳化物化学位移的增加揭示了通过碳化物桥的相互作用减弱。对于桥连碳化物配体，与铂的化学位移和耦合常数呈线性相关，母体RuC的NMR数据符合这种关系，提供了一种相对于解离的RuC确定RuC-Pt键强度的光谱方法。Ru≡C-Pt-L片段相对于L的特性的柔韧性将碳化物桥连配合物确立为配体供体能力的范围广泛且灵敏的探针。
