Coordination chemistry of N-heterocyclic nitrenium-based ligands.
Coordination chemistry of N-heterocyclic nitrenium-based ligands.
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DOI：
10.1002/chem.201405526
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发表时间：
2015-05
期刊：
影响因子：
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通讯作者：
Yuri Tulchinsky;S. Kozuch;P. Saha;Assaf Mauda;G. Nisnevich;M. Botoshansky;L. Shimon;Mark Gandelman
中科院分区：
文献类型：
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作者：
Yuri Tulchinsky;S. Kozuch;P. Saha;Assaf Mauda;G. Nisnevich;M. Botoshansky;L. Shimon;Mark Gandelman
对三齿氮配体的配位性质进行了全面的研究。N-杂环氮鎓离子表现出与各种过渡金属的一般和通用结合能力，如基于这些不寻常配体的Rh（I）、Rh（III）、Mo（0）、Ru（0）、Ru（II）、Pd（II）、Pt（II）、Pt（IV）和Ag（I）络合物的合成和表征所例示。氮-金属键的形成在溶液中通过选择性（15）N-标记实验和在固态中通过X射线晶体学都明确地证实。作为配体的N-杂环氮鎓的一般性也通过系统的DFT研究其对所有第二行过渡和后过渡金属（Y-Cd）的亲和力在相应的键离解能方面进行了验证。
Comprehensive studies on the coordination properties of tridentate nitrenium-based ligands are presented. N-heterocyclic nitrenium ions demonstrate general and versatile binding abilities to various transition metals, as exemplified by the synthesis and characterization of Rh(I) , Rh(III) , Mo(0) , Ru(0) , Ru(II) , Pd(II) , Pt(II) , Pt(IV) , and Ag(I) complexes based on these unusual ligands. Formation of nitrenium-metal bonds is unambiguously confirmed both in solution by selective (15) N-labeling experiments and in the solid state by X-ray crystallography. The generality of N-heterocyclic nitrenium as a ligand is also validated by a systematic DFT study of its affinity towards all second-row transition and post-transition metals (Y-Cd) in terms of the corresponding bond-dissociation energies.