Theoretical study of Rh(I) and Rh(III) bis(isonitrile) complexes as promising reagents for synthesis of N-heterocyclic carbenes

• Published in: Russian journal of inorganic chemistry Vol. 57; no. 12; pp. 1576 - 1583
• Main Authors: Novikov, A. S., Dement’ev, A. I., Medvedev, Yu. N.
• Format: Journal Article
• Language: English
• Published: Dordrecht SP MAIK Nauka/Interperiodica 01.12.2012
• Subjects: Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Theoretical Inorganic Chemistry; Electrophilic Attack; Dppe; Nucleophilic Addition; Natural Bond Orbital; Cycloaddition Reaction
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023612120157

The properties of the [RhCl(PH 3 )(CNMe) 2 ] and [RhCl 3 (PH 3 )(CNMe) 2 ] complexes (relative stability of different isomers, structural features, vibrational frequencies, bond nature, atomic charge distribution, and well as analysis of the MO composition and energies) have been studied by quantum-chemical methods. For the [RhCl(PH 3 )(CNMe) 2 ] complex, the cis isomer is the most stable one; for the [RhCl 3 (PH 3 )(CNMe) 2 ] complex, the cis-mer isomer is the most stable one. In the [RhCl(PH 3 )(CNMe) 2 ] complex, the moderate π back-donation effect is observed. The coordination of C≡NMe to the metal should lead to activation of the ligand in nucleophilic addition and cycloaddition reactions with a normal electron distribution and hinder the electrophilic attack at the N atom of isonitrile.