Ab initio accelerated molecular dynamics study of the hydride ligands in the ruthenium complex: Ru(H2)2H2(P(C5H9)3)2

Marco Lauricella; Letizia Chiodo; Giovanni Ciccotti; Alberto Albinati

doi:10.1039/c9cp03776d

Ab initio accelerated molecular dynamics study of the hydride ligands in the ruthenium complex: Ru(H₂)₂H₂(P(C₅H₉)₃)₂

Phys Chem Chem Phys. 2019 Dec 7;21(45):25247-25257. doi: 10.1039/c9cp03776d. Epub 2019 Nov 7.

Authors

Marco Lauricella¹, Letizia Chiodo², Giovanni Ciccotti³, Alberto Albinati⁴

Affiliations

¹ Istituto per le Applicazioni del Calcolo IAC-CNR, Via dei Taurini 19, 00185, Rome, Italy.
² Department of Engineering, Campus Bio-Medico University of Rome, Via Álvaro del Portillo 21, 00128, Rome, Italy. l.chiodo@unicampus.it.
³ Istituto per le Applicazioni del Calcolo IAC-CNR, Via dei Taurini 19, 00185, Rome, Italy and Physics Department, University of Rome La Sapienza, Ple. A. Moro 5, 00185 Roma, Italy and School of Physics, University College of Dublin, Belfield, Dublin 4, Ireland.
⁴ Chemistry Department, Milan University, Via C. Golgi 19, 20133, Milan, Italy.

PMID: 31697300
DOI: 10.1039/c9cp03776d

Abstract

The dihydrogen complex Ru(H₂)₂H₂(P(C₅H₉)₃)₂ has been investigated, via ab initio accelerated molecular dynamics, to elucidate the H ligands dynamics and possible reaction paths for H₂/H exchange. We have characterized the free energy landscape associated with the H atoms positional exchange around the Ru centre. From the free energy landscape, we have been able to estimate a barrier of 6 kcal mol^-1 for the H₂/H exchange process. We have also observed a trihydrogen intermediate as a passing state along some of the possible reaction pathways.