Trinuclear and Tetranuclear Ruthenium Carbonyl Nitrosyls: Oxidation of a Carbonyl Ligand by an Adjacent Nitrosyl Ligand

Author:

Chen Shengchun1ORCID,Feng Xuejun12,Xie Yaoming2ORCID,King R. Bruce2ORCID,Schaefer Henry F.2ORCID

Affiliation:

1. School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China

2. Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA

Abstract

Trinuclear and tetranuclear ruthenium carbonyls of the types Ru3(CO)n(NO)2, Ru3(N)(CO)n(NO), Ru3(N)2(CO)n, Ru3(N)(CO)n(NCO), Ru3(CO)n(NCO)(NO), Ru4(N)(CO)n(NO), Ru4(N)(CO)n(NCO), and Ru4(N)2(CO)n related to species observed experimentally in the chemistry of Ru3(CO)10(µ-NO)2 have been investigated using density functional theory. In all cases, the experimentally observed structures have been found to be low-energy structures. The low-energy trinuclear structures typically have a central strongly bent Ru–Ru–Ru chain with terminal CO groups and bridging nitrosyl, isocyanate, and/or nitride ligands across the end of the chain. The low-energy tetranuclear structures typically have a central Ru4N unit with terminal CO groups and a non-bonded pair of ruthenium atoms bridged by a nitrosyl or isocyanate group.

Funder

Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University

Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University in China

U.S. Department of Energy, Basic Energy Sciences, Division of Chemistry, Computational and Theoretical Chemistry (CTC) Program

Publisher

MDPI AG

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