Md. Monir Hossain , Vladimir N. Nesterov , Graeme Hogarth , German E. Pieslinger , Shariff E. Kabir , Shishir Ghosh
{"title":"Ru-Sn and Ru-Os mixed-metal clusters bearing heterocyclic thiolate ligand(s): Synthesis, crystal and electronic structures","authors":"Md. Monir Hossain , Vladimir N. Nesterov , Graeme Hogarth , German E. Pieslinger , Shariff E. Kabir , Shishir Ghosh","doi":"10.1016/j.jorganchem.2025.123593","DOIUrl":null,"url":null,"abstract":"<div><div>The synthesis of [Ru<sub>2</sub>(CO)<sub>4</sub>(SnMe<sub>3</sub>)<sub>2</sub>(µ-L)<sub>2</sub>] (<strong>1–2</strong>) (<strong>1</strong>, <em>L</em> = pySH = pyridine-2-thiol; <strong>2</strong>, <em>L</em> = pymSH = pyrimidine-2-thiol) and their reactions with [M<sub>3</sub>(CO)<sub>10-n</sub>(NCMe)<sub>n</sub>] (<em>M</em> = Ru, Os; <em>n</em> = 0, 2) are described. Ru<sub>2</sub>Sn<sub>2</sub> clusters are prepared in moderate yields from the one-pot reaction of [Ru<sub>3</sub>(CO)<sub>12</sub>], Me<sub>3</sub>SnCl and pySH in the presence of KOH, and each contains two [Ru(CO)<sub>2</sub>(SnPh<sub>3</sub>)] units bridged by a pair of heterocyclic thiolate ligands. Treatment of <strong>1</strong>–<strong>2</strong> with [Ru<sub>3</sub>(CO)<sub>12</sub>] in boiling benzene affords pentaruthenium clusters [Ru<sub>5</sub>(CO)<sub>16</sub>(µ<sub>3</sub>-L)(µ<sub>4</sub>-SnMe)] (<strong>3–4</strong>) containing a raft-like metallic core consisting of five ruthenium and one tin atom. In contrast, reactions of <strong>1</strong>–<strong>2</strong> with [Os<sub>3</sub>(CO)<sub>10</sub>(NCMe)<sub>2</sub>] yield tetranuclear clusters [RuOs<sub>3</sub>(CO)<sub>12</sub>(η<sup>1</sup>-Me)(µ<sub>3</sub>-L)] (<strong>5</strong>, <em>L</em> = pyS; <strong>7</strong>, <em>L</em> = pymS) as the major products, in which the four metal atoms adopt a butterfly geometry, with the ruthenium occupying a wingtip position. Further products including [RuOs<sub>3</sub>(CO)<sub>12</sub>(µ<sub>3</sub>-pyS)(µ-H)] (<strong>6</strong>) and [Os<sub>4</sub>(CO)<sub>12</sub>(µ<sub>3</sub>-pymS)(η<sup>1</sup>-Me)] (<strong>8</strong>) are also isolated from these reactions. Clusters <strong>6</strong> and <strong>8</strong> possess an M<sub>4</sub> butterfly skeleton, with ruthenium in a hinge position in mixed-metal cluster <strong>6</strong>. The molecular structure of each product has been established by XRD analysis, and the bonding in these clusters has been investigated by electronic structure calculations.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123593"},"PeriodicalIF":2.1000,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X25000877","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The synthesis of [Ru2(CO)4(SnMe3)2(µ-L)2] (1–2) (1, L = pySH = pyridine-2-thiol; 2, L = pymSH = pyrimidine-2-thiol) and their reactions with [M3(CO)10-n(NCMe)n] (M = Ru, Os; n = 0, 2) are described. Ru2Sn2 clusters are prepared in moderate yields from the one-pot reaction of [Ru3(CO)12], Me3SnCl and pySH in the presence of KOH, and each contains two [Ru(CO)2(SnPh3)] units bridged by a pair of heterocyclic thiolate ligands. Treatment of 1–2 with [Ru3(CO)12] in boiling benzene affords pentaruthenium clusters [Ru5(CO)16(µ3-L)(µ4-SnMe)] (3–4) containing a raft-like metallic core consisting of five ruthenium and one tin atom. In contrast, reactions of 1–2 with [Os3(CO)10(NCMe)2] yield tetranuclear clusters [RuOs3(CO)12(η1-Me)(µ3-L)] (5, L = pyS; 7, L = pymS) as the major products, in which the four metal atoms adopt a butterfly geometry, with the ruthenium occupying a wingtip position. Further products including [RuOs3(CO)12(µ3-pyS)(µ-H)] (6) and [Os4(CO)12(µ3-pymS)(η1-Me)] (8) are also isolated from these reactions. Clusters 6 and 8 possess an M4 butterfly skeleton, with ruthenium in a hinge position in mixed-metal cluster 6. The molecular structure of each product has been established by XRD analysis, and the bonding in these clusters has been investigated by electronic structure calculations.
期刊介绍：
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
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