三核和四核羰基亚硝酰钌：相邻亚硝酰配体对羰基配体的氧化作用。

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

作者信息

Chen Shengchun, Feng Xuejun, Xie Yaoming, King R Bruce, Schaefer Henry F

机构信息

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

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

出版信息

Molecules. 2024 Sep 3;29(17):4165. doi: 10.3390/molecules29174165.

DOI:10.3390/molecules29174165

PMID:39275013

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11397334/

Abstract

Trinuclear and tetranuclear ruthenium carbonyls of the types Ru(CO)(NO), Ru(N)(CO)(NO), Ru(N)(CO), Ru(N)(CO)(NCO), Ru(CO)(NCO)(NO), Ru(N)(CO)(NO), Ru(N)(CO)(NCO), and Ru(N)(CO) related to species observed experimentally in the chemistry of Ru(CO)(µ-NO) 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 RuN unit with terminal CO groups and a non-bonded pair of ruthenium atoms bridged by a nitrosyl or isocyanate group.

摘要

已使用密度泛函理论研究了与在Ru(CO)(µ-NO)化学中实验观察到的物种相关的Ru(CO)(NO)、Ru(N)(CO)(NO)、Ru(N)(CO)、Ru(N)(CO)(NCO)、Ru(CO)(NCO)(NO)、Ru(N)(CO)(NO)、Ru(N)(CO)(NCO)和Ru(N)(CO)类型的三核和四核钌羰基化合物。在所有情况下，实验观察到的结构均为低能量结构。低能量三核结构通常具有中心强烈弯曲的Ru-Ru-Ru链，链端带有末端CO基团以及横跨链端的桥连亚硝酰基、异氰酸酯和/或氮化物配体。低能量四核结构通常具有带有末端CO基团的中心RuN单元以及由亚硝酰基或异氰酸酯基团桥连的一对非键合钌原子。