Design, Synthesis, and Structural Analysis of Divalent NI Compounds and Identification of a New Electron-Donating Ligand

• Published in: Chemistry : a European journal 2016-01, Vol.22 (3), p.1088-1096
• Main Authors: Bharatam, Prasad V., Arfeen, Minhajul, Patel, Neha, Jain, Priyanka, Bhatia, Sonam, Chakraborti, Asit K., Khullar, Sadhika, Gupta, Vijay, Mandal, Sanjay K.
• Format: Article
• Language: English
• Subjects: carbene ligands; Chemical speciation; Chemical synthesis; Chemistry; density functional calculations; Design; Design analysis; Exploration; ligand design; Ligands; Nickel compounds; nitrogen; Quantum chemistry; Spectra; Structural analysis; X-ray diffraction
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201503618

The dative‐bond representation (L→E) in compounds with main group elements (E) has triggered extensive debate in the recent past. The scope and limits of this nonclassical coordination bond warrant comprehensive exploration. Particularly compounds with (L→N←L′)+ arrangement are of special interest because of their therapeutic importance. This work reports the design and synthesis of novel chemical species with the general structural formula (L→N←L′)+ carrying the unusual ligand cyclohexa‐2,5‐diene‐4‐(diaminomethynyl)‐1‐ylidene. Four species belonging to the (L→N←L′)+ class carrying this unconventional ligand were synthesized. Quantum chemical and X‐ray diffraction analyses showed that the electronic and geometric parameters are consistent with those of already reported divalent NI compounds. The molecular orbital analysis, geometric parameters, and spectral data clearly support the L→N and N←L′ interactions in these species. The newly identified ligand has the properties of a reactive carbene and high nucleophilicity. Divalent by design: Novel systems, in which an N+ center is flanked by electron‐donating benzimidazole/benzothiazole and cyclohexa‐2,5‐diene‐4‐(diaminomethynyl)‐1‐ylidene ligands, were designed and synthesized (see figure). Crystal, structure and electronic, structure analysis confirmed the presence of dative bond between electron‐donating ligands and the N+ center.