Henry U. Valle

CCC-NHC Pincer Zr Diamido Complexes: Synthesis, Characterisation, and Catalytic Activity in Hydroamination/Cyclisation of Unactivated Amino-Alkenes, -Alkynes, and Allenes*

2-(1,3-Bis-3′-butylimidazol-1′-yl-2′-ylidene)phenylene)bis(dimethylamido) iodo zirconium(iv) (3) and 2-(1,3-bis-3′-butylimidazol-1′-yl-2′-ylidene)phenylene)bis (dimethylamido) bromo zirconium(iv) (4), have been prepared via a modification of the solvent and stoichiometry from the previously reported methodology. The reactivity of 3 and 4 in hydroamination/cyclisation is reported. Both diamido complexes have been found to improve catalytic activity as compared with the previously reported mono-amido analogues. Complexes 3 and 4 were observed to be selective for primary amines over secondary amines in hydroamination/cyclisation. The lack of reactivity with secondary amines is consistent with a mechanism involving requisite formation of a Zr-imido intermediate.

Crystal structure of tris-(di-methyl-amido-κN)-bis-(di-methyl-amine-κN)-zirconium(IV) iodide.

The crystal structure of tris(dimethylamido)bis(dimethylamine) zirconium(IV) iodide is reported.

CCDC 1554489: Experimental Crystal Structure Determination

Related Article: Hui Zhou, Hetti Handi Chaminda Lakmal, Jonathan M. Baine, Henry U. Valle, Xue Xu, Xin Cui||Chemical Science|||doi:10.1039/C7SC02576A

CCDC 1538722: Experimental Crystal Structure Determination

Related Article: Hui Zhou, Hetti Handi Chaminda Lakmal, Jonathan M. Baine, Henry U. Valle, Xue Xu, Xin Cui||Chemical Science|||doi:10.1039/C7SC02576A