TY - JOUR

T1 - Theoretical study of Rh(I) and Rh(III) bis(isonitrile) complexes as promising reagents for synthesis of N-heterocyclic carbenes

AU - Novikov, A. S.

AU - Dement'Ev, A. I.

AU - Medvedev, Yu N.

PY - 2012/1/1

Y1 - 2012/1/1

N2 - The properties of the [RhCl(PH3)(CNMe)2] and [RhCl3(PH3)(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(PH3)(CNMe)2] complex, the cis isomer is the most stable one; for the [RhCl3(PH3)(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.

AB - The properties of the [RhCl(PH3)(CNMe)2] and [RhCl3(PH3)(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(PH3)(CNMe)2] complex, the cis isomer is the most stable one; for the [RhCl3(PH3)(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.

UR - http://www.scopus.com/inward/record.url?scp=84874624854&partnerID=8YFLogxK

U2 - 10.1134/S0036023612120157

DO - 10.1134/S0036023612120157

M3 - Article

AN - SCOPUS:84874624854

VL - 57

SP - 1576

EP - 1583

JO - Russian Journal of Inorganic Chemistry

JF - Russian Journal of Inorganic Chemistry

SN - 0036-0236

IS - 12

ER -