M–Ru–Sn (M = Re, Mn) heterometallic and Ru–Sn bimetallic carbonyl complexes bearing heterocyclic thiolato ligands

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2025-06-26 DOI:10.1016/j.poly.2025.117653

Shahin A. Begum , Md. Monir Hossain , Md. Arshad H. Chowdhury , Joyanta K. Saha , Vladimir N. Nesterov , German E. Pieslinger , Tareque S.M. Abedin , Shariff E. Kabir

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Abstract

The present study reports the synthesis and characterization of some heterogenic tri- and bimetallic carbonyl complexes of Re, Ru, Mn, and Sn containing heterocyclic thiolato ligands. Three new heterometallic complexes [ReRu(CO)₅(Ph₃Sn)(μ-pyS)(μ-MBT)] (5), [ReRu(CO)₅(Ph₃Sn)(μ-pyS)₂] (6) and [MnRu(CO)₅(Ph₃Sn)(μ-pyS)₂] (7) bearing bridging heterocyclic thiolato ligands (pyS = pyridine-2-thiolato; MBT = 2-mercaptobenzothiolato) were obtained from the reactions of [Ru₂(CO)₄(Ph₃Sn)₂(μ-pyS)₂] (1) with each of [Re₂(CO)₆(μ-MBT)₂] (2), [Re₂(CO)₆(μ-pyS)₂] (3) and [Mn₂(CO)₆(μ-pyS)₂] (4) respectively in CH₂Cl₂ at room temperature. The identity of 7 was further substantiated by its reaction with PPh₃, which produced the previously reported mononuclear complexes [Ru(CO)₂(Ph₃Sn)(PPh₃)(pyS)] and [Mn(CO)₃(PPh₃)(pyS)]. Compound 1 reacts with bidentate nitrogen donor ligands, 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) at room temperature, to produce the κ¹(S)-coordinated pyridine-2-thiolato and κ²(N)- chelating phen or bipy complexes [Ru(CO)₂(SnPh₃)(κ²-phen)-{κ¹-(S)-pyS}] (8) and [Ru(CO)₂(SnPh₃)(κ²-bipy){κ¹-(S)-pyS}] (9), respectively. Heterobifunctional monophosphines, such as tri(2-furyl)phosphine (PFu₃) and tris(2-thienyl)phosphine (PTh₃), and diphosphines such as dppm [bis(diphenylphosphino)methane] react with 1 to give homologous compounds [Ru(CO)₂(SnPh₃)(PFu₃)(κ²-pyS)] (10), [Ru(CO)₂(SnPh₃)(PTh₃)(κ²-pyS)] (11) and [Ru(CO)₂(SnPh₃)(κ¹-dppm)(κ²-pyS)] (12), respectively, in which the pyS ligands chelate through the S and N atoms. All the new compounds, 5–12, were characterized based on their elemental analyses, IR, and NMR spectroscopy. In addition, the molecular structures of four representative compounds (5, 8, 10, and 12) were unambiguously established by single-crystal X-ray diffraction analysis. The bonding in these complexes, together with starting dimers 1 and 2, has been investigated by electronic structure calculations.

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M - Ru-Sn （M = Re, Mn）异质金属和Ru-Sn双金属羰基配合物含杂环硫腙配体

本文报道了稀土、钌、锰、锡等含杂环硫腙配体的异相三金属和双金属羰基配合物的合成和表征。三种新型杂金属配合物[ReRu(CO)5(Ph3Sn)(μ-pyS)(μ-MBT)] (5), [ReRu(CO)5(Ph3Sn)(μ-pyS)2](6)和[MnRu(CO)5(Ph3Sn)（μ-pyS)2](7)）为桥接杂环硫代配体(pyS = 吡啶-2-硫代；[Ru2(CO)4(Ph3Sn)2(μ-pyS)2](1)在CH2Cl2中分别与[Re2(CO)6(μ-MBT)2](2)、[Re2(CO)6(μ-pyS)2](3)和[Mn2(CO)6(μ-pyS)2](4)反应，制得MBT = 2-巯基苯并噻唑酸盐。7与PPh3的反应进一步证实了它的身份，生成了先前报道的单核配合物[Ru(CO)2(Ph3Sn)(PPh3)(pyS)]和[Mn(CO)3(PPh3)(pyS)]。化合物1与双齿氮供体1,10-菲罗啉（phen）或2,2′-联吡啶（bipy）在室温下反应，分别生成κ1(S)-配位吡啶-2-硫代嘌呤和κ2(N)-螯合吩或bipy配合物[Ru(CO)2(SnPh3)(κ2-phen)-{κ1-(S)- pys}](8)和[Ru(CO)2(SnPh3)(κ2-bipy){κ1-(S)- pys}](9)。异双功能单膦，如三（2-呋喃基）膦（PFu3）和三（2-噻吩基）膦（PTh3），和二膦，如dppm[双（二苯基膦）甲烷]与1反应，分别得到同源化合物[Ru(CO)2(SnPh3)(PFu3)(κ2-pyS)] (10), [Ru(CO)2(SnPh3)(PTh3)(κ2-pyS)]（11）和[Ru(CO)2(SnPh3)(κ1-dppm)(κ2-pyS)](12)，其中pyS配体通过S和N原子进行螯合。所有新化合物（5-12）均通过元素分析、红外光谱和核磁共振光谱进行了表征。此外，通过单晶x射线衍射分析，确定了4个具有代表性的化合物（5、8、10和12）的分子结构。用电子结构计算研究了这些配合物与二聚体1和2的成键。

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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.

M–Ru–Sn (M = Re, Mn) heterometallic and Ru–Sn bimetallic carbonyl complexes bearing heterocyclic thiolato ligands

Abstract

M–Ru–Sn (M = Re, Mn) heterometallic and Ru–Sn bimetallic carbonyl complexes bearing heterocyclic thiolato ligands