Facile Os-Os bond cleavage in the reactions of [Os3(CO)10(NCMe)2] and [Os3(CO)10(μ-H)2] with tetramethylthiuram disulfide (tmtd): Syntheses and crystal structures of new polynuclear osmium carbonyl complexes containing a dimethyldithiocarbamate ligand(s)

doi:10.1016/j.jorganchem.2020.121133

Journal of Organometallic Chemistry

Volume 911, 1 April 2020, 121133

https://doi.org/10.1016/j.jorganchem.2020.121133 Get rights and content

Highlights

•
Reactions of [Os₃(CO)₁₀(NCMe)₂] and [Os₃(CO)₁₀(μ-H)₂] with tetramethylthiuram disulfide [(Me₂NCS₂)₂].
•
Synthesis and structure of triosmium complex containing dimethyldithiocarbamate ligands [Me₂NCS₂].
•
Synthesis and structure of tetraosmium complex containing a triply bridging CO₂ ligand.
•
Synthesis and structure of triosmium complex containing dimethylthiocarbamate ligand [Me₂NC(O)S].
•
Sythesis and structure of hydrido-triosmium clusters containing dimethyldithiocarbamate ligand.

Abstract

The reaction of the labile triosmium cluster [Os₃(CO)₁₀(NCMe)₂] with tetramethylthiuram disulfide [(Me₂NCS₂)₂, tmtd] has been investigated at room temperature. Conducting the reaction under mild conditions has permitted the isolation of the three new polynuclear osmium complexes [Os₃(CO)₁₀{κ²(S,S)-S₂CNMe₂}₂] (1), [Os₄(CO)₁₂{κ²(S,S)-S₂CNMe₂}₂{μ₃-η¹(C),κ²(O,O)-CO₂)}(μ₃-S)] (2) and [Os₃(CO)₉{μ₃-η¹(C),κ¹(S)-SCNMe₂}{μ-κ¹(S)-SC(O)NMe₂}] (3) in 20, 16 and 10% yield, respectively, in addition to the known mononuclear complex [Os(CO)₂{κ²(S,S)-S₂CNMe₂}₂] (4) in 10% yield. The triosmium complex 1 has a linear arrangement of osmium atoms with each terminal osmium center containing a chelating Me₂NCS₂ ligand. The tetraosmium complex 2 also possesses a μ₃-CO₂ ligand in addition to capping sulfido and chelating Me₂NCS₂ ligands. Complex 3 contains an open triosmium core with the open Os···Os edge bridged by a Me₂NC(O)S ligand and a capping Me₂NCS ligand. A similar reaction between the unsaturated cluster [Os₃(CO)₁₀(μ-H)₂] and [(Me₂NCS₂)₂] yielded the triosmium complexes [Os₃(CO)₁₀{μ-κ¹(S)-S₂CNMe₂}(μ-H)] (5) and [Os₃(CO)₉{μ₃-κ²(S,S)-S₂CNMe₂}(μ-H)] (6) in addition to compounds 1 and 4 and the known hydroxyl cluster [Os₃(CO)₁₀(μ-OH)(μ-H)] (7) in 7, 14, 14, 10, and 6% yield, respectively. Both 5 and 6 possess a triosmium core, and the Me₂NCS₂ ligand acts in edge-bridging capacity in the former while it serves as a face-capping ligand in the latter. All new complexes have been characterized by combustion analyses and IR and NMR spectroscopies, and the solid-state structures of 1–3, and 6 have been established by X-ray crystallography. The bonding in clusters 1-3 and 6 has been examined by electronic structure calculations, and the thermodynamics for the formation of 1 and MeCN (two equiv) from [Os₃(CO)₁₀(MeCN)₂] and tmtd, relative to other chelated and bridged isomers of [Os₃(CO)₁₀(tmtd)] are discussed.

Graphical abstract

Introduction

Dithiocarbamates are widely used in inorganic chemistry as a 3-electron donor that can stabilize metal centers in a variety of oxidation states [[1], [2], [3], [4], [5]]. Consequently, a large number of transition metal dithiocarbamate complexes are known, some of which find use in applications as key device components in materials science, as well as medicine and agriculture [1,2]. Although dithiocarbamate donors generally function as robust bidentate ligands and act in a simple spectator fashion, it is becoming increasingly apparent that this is not always the case since such ligands have been found to act in a non-innocent fashion in an increasing number of instances. For example, the formation of sulfido and thiocarboxamide ligands via a single carbon-sulfur bond cleavage of dithiocarbamates have been reported over the last four decades [6], while more recently double carbon-sulfur cleavage has been observed leading to the generation of multiple sulfido and an aminoalkylidyne ligands [[7], [8]]. These same carbon-sulfur bond cleavage reactions have been successfully exploited for the preparation of metal sulfide nanoparticles [9,10]. Finally, several studies on transition metal dithiocarbamate complexes as anticancer agents have also drawn considerable attraction [11].

Although numerous examples of mono, di and polynuclear iron and ruthenium dithiocarbamate complexes have been reported in the literature [1,5,12], dithiocarbamate complexes of osmium, which provide the greatest range of oxidation states in the Group 8 compounds that contain an ancillary dithiocarbamate ligand, remain relatively limited [1,[13], [14], [15], [16]]. Most of these osmium complexes contain either a mono or dinuclear framework. To our knowledge, only two polynuclear osmium complexes containing a dithiocarbamate ligand have been reported, and these products were isolated from the reaction of the vinyloxy-compound [HOs₃(CO)₁₀(μ-OCH=CH₂)] with [Et₄N][S₂CNEt₂] at −78 °C [14,15]. Here the initial product of substitution is [HOs₃(CO)₁₀{μ-κ¹(S)-S₂CNEt₂}], which decarbonylates upon heating in refluxing heptane to give [HOs₃(CO)₉{μ₃-κ²(S,S)-S₂CNEt₂}] (Scheme 1) [14,15].

While numerous synthetic routes exist for the preparation of new dithiocarbamate-substituted polynuclear osmium complexes, the use of thiuram disulfides as a convenient source for the delivery of a dithiocarbamate ligand(s) stands out for its convenience [17]. Using this strategy, Karim and Hogarth isolated a series of mononuclear osmium(II)-bis(dithiocarbamate) complexes of the general formula [Os(CO)₂{κ²(S,S)-S₂CNR₂}₂] instead of the desired triosmium complexes [Os₃(CO)_10,9{κ²(S,S)-S₂CR₂}] from the reactions of [Os₃(CO)₁₀L₂] (L = CO, MeCN) with thiuram disulfides [16], as illustrated in Scheme 2. Surprisingly, no polynuclear osmium compounds were found in these reactions that were conducted under relatively mild conditions. These results indicate that the expected Os₃-based intermediates are not stable under the temperatures employed in the reaction, decomposing to the mononuclear [Os(CO)₂{κ²(S,S)-S₂CNR₂}₂] species. Wishing to probe the nature of the initial substitution product in the reaction of [Os₃(CO)₁₀(NCMe)₂] with a thiuram ligand, we have reinvestigated this reaction using tetramethylthiuram disulfide as the sulfur-delivery agent at room temperature. In addition, we have also investigated the reaction between [Os₃(CO)₁₀(μ-H)₂] and [(Me₂NCS₂)₂] in order to synthesize the Me₂NCS₂ analogues of the hydrido clusters as shown in Scheme 1. Herein we report the successful isolation and structural characterization of five new polynuclear osmium complexes in addition to the known mononuclear compound [Os(CO)₂{κ²(S,S)-S₂CNMe₂}₂] (4).

Section snippets

General remarks

All reactions were carried out under an inert atmosphere of nitrogen using standard Schlenk techniques unless otherwise stated, and reagent grade solvents were dried by the standard methods and freshly distilled prior to use. [Os₃(CO)₁₂] was purchased from Strem Chemical Inc. and used without further purification. Tetramethylthiuram disulfide [(Me₂NCS₂)₂, tmtd] was purchased from Acros Organics and used as received. The starting cluster [Os₃(CO)₁₀(NCMe)₂] [18] was prepared according to the

Reaction of [Os₃(CO)₁₀(NCMe)₂] with tetramethylthiuram disulfide [(Me₂NCS₂)₂]

The labile cluster [Os₃(CO)₁₀(NCMe)₂] reacts with two equivalents of tetramethylthiuram disulfide [(Me₂NCS₂)₂] at room temperature to give the three new polynuclear osmium complexes [Os₃(CO)₁₀{κ²(S,S)-S₂CNMe₂}₂] (1), [Os₄(CO)₁₂{κ²(S,S)-S₂CNMe₂}₂{μ₃-η¹(C),κ²(O,O)-CO₂}(μ₃-S)] (2) and [Os₃(CO)₉{μ₃-η¹(C),κ¹(S)-SCNMe₂}{μ-κ¹(S)-SC(O)NMe₂}] (3) in 20, 16, and 10% yield, respectively (Scheme 3). All three new complexes were structurally characterized by single-crystal X-ray diffraction analysis and in

Conclusions

Five new polynuclear osmium complexes namely [Os₃(CO)₁₀{κ²(S,S)-S₂CNMe₂}₂] (1), [Os₄(CO)₁₂{κ²(S,S)-S₂CNMe₂}₂{μ₃-η¹(C),κ²(O,O)-CO₂}(μ₃-S)] (2), [Os₃(CO)₉{μ₃-η¹(C),κ¹(S)-SCNMe₂}{μ-κ¹(S)-SC(O)NMe₂}] (3), [Os₃(CO)₁₀{μ-κ¹(S)-S₂CNMe₂}(μ-H)] (5), and [Os₃(CO)₉{μ₃-κ²(S,S)-S₂CNMe₂}(μ-H)] (6) have been isolated from the room temperature reactions of [Os₃(CO)₁₀(NCMe)₂] and [Os₃(CO)₁₀(μ-H)₂] with tetramethylthiuram disulfide (tmtd), and the molecular structure of each new product, except for 5, was

Acknowledgments

Financial support from the Ministry of Education, the Government of the People’s Republic of Bangladesh (SG and SEK) and the Robert A. Welch Foundation (Grant B-1093-MGR) is acknowledged. The DFT calculations were performed at UNT through CASCaM, which is an NSF-supported facility (CHE-1531468).

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Facile Os-Os bond cleavage in the reactions of [Os3(CO)10(NCMe)2] and [Os3(CO)10(μ-H)2] with tetramethylthiuram disulfide (tmtd): Syntheses and crystal structures of new polynuclear osmium carbonyl complexes containing a dimethyldithiocarbamate ligand(s)

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

General remarks

Reaction of [Os3(CO)10(NCMe)2] with tetramethylthiuram disulfide [(Me2NCS2)2]

Conclusions

Acknowledgments

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Inorg. Chem.

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Inorg. Chem.

J. Chem. Soc., Dalton Trans.

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J. Am. Chem. Soc.

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Chem. Mater.

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Acta Chim. Acad. Sci. Hung.

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Z. Anorg. Allg. Chem.

Facile Os-Os bond cleavage in the reactions of [Os₃(CO)₁₀(NCMe)₂] and [Os₃(CO)₁₀(μ-H)₂] with tetramethylthiuram disulfide (tmtd): Syntheses and crystal structures of new polynuclear osmium carbonyl complexes containing a dimethyldithiocarbamate ligand(s)

Reaction of [Os₃(CO)₁₀(NCMe)₂] with tetramethylthiuram disulfide [(Me₂NCS₂)₂]