Reactions of [Ru3(CO)10(µ-dppe)] towards tetramethylthiourea and N,N′-diisopropylthiourea: Generation of tri- and tetraruthenium carbonyl clusters bearing bridging/chelating dppe, triply/quadruply bridging sulfido and aminocarbene ligands

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2025-01-20 DOI:10.1016/j.poly.2025.117411

Md. Nazmul Huda , Md. Abdullah Al Mamun , Joyanta K. Saha , Vladimir N. Nesterov , Tareque S.M. Abedin , Shariff E. Kabir

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Abstract

Two new sulfur-capped ruthenium clusters, a triruthenium [Ru₃(CO)₇(μ-dppe)(μ₃-S)₂] (1) (41% yield) and a tetraruthenium [Ru₄(CO)₆(µ-CO)₂{η¹-C(NMe₂)₂}(κ²-dppe)(µ₄-S)₂] (2) (15% yield) were obtained from the reaction of dppe-bridged triruthenium cluster [Ru₃(CO)₁₀(μ-dppe)] [dppe = 1,2-bis(diphenylhosphino)ethane] with four equivalents of tetramethylthiourea in THF at reflux. A similar reaction with N,N′-diisopropylthiourea in the same solvent and temperature exclusively afforded 1. Cluster 1 comprises an open Ru₃S₂ core capped by two μ₃-sulfido ligands resulting from activation of the C–S bond of the thiourea ligand, and the dppe ligand bridges the open Ru….Ru edge occupying axial sites. Cluster 2 provides a unique example of a Ru₄S₂ skeleton with a square-planar arrangement of the four ruthenium atoms, two quadruply bridging sulfido ligands on opposite faces of the cluster, a terminally coordinated tetramethyldiaminocarbene ligand, formed by desulfurization of tetramethylthiourea ligand, a chelating dppe and two bridging carbonyl ligands on adjacent Ru–Ru vectors. The molecular structures of 1 and 2 have been determined by spectroscopic (IR, ¹H NMR, and ³¹P{¹H} NMR) data and single-crystal X-ray diffraction analysis. The bonding of these new compounds has been examined using DFT optimization and topological analysis using atoms in molecules (AIM) quantum theory.

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.