TY - JOUR
T1 - In silico switch from second- to first-row transition metals in olefin metathesis
T2 - From Ru to Fe and from Rh to Co
AU - Luque-Urrutia, Jesús Antonio
AU - Gimferrer, Martí
AU - Casals-Cruañas, Èric
AU - Poater i Teixidor, Albert
N1 - Publisher Copyright:
© 2017 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2017/12/14
Y1 - 2017/12/14
N2 - Density functional theory (DFT) calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru) and 9 (Co and Rh) in an already well-known catalytic mechanism, which is based on an Ru(SIMes)(PPh3)Cl2=CH(Ph) complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate.
AB - Density functional theory (DFT) calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru) and 9 (Co and Rh) in an already well-known catalytic mechanism, which is based on an Ru(SIMes)(PPh3)Cl2=CH(Ph) complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate.
KW - Catalysis
KW - Cobalt
KW - Density functional theory
KW - Iron
KW - N-heterocyclic carbene
KW - Olefin metathesis
KW - Reaction mechanism
KW - Rhodium
KW - Ruthenium
UR - http://www.scopus.com/inward/record.url?scp=85040582715&partnerID=8YFLogxK
U2 - 10.3390/catal7120389
DO - 10.3390/catal7120389
M3 - Article
AN - SCOPUS:85040582715
VL - 7
JO - Catalysts
JF - Catalysts
SN - 2073-4344
IS - 12
M1 - 389
ER -