Photocatalytic H2-Evolution by Homogeneous Molybdenum Sulfide Clusters Supported by Dithiocarbamate Ligands

Patricia R Fontenot; Bing Shan; Bo Wang; Spenser Simpson; Gayathri Ragunathan; Angelique F Greene; Antony Obanda; Leigh Anna Hunt; Nathan I Hammer; Charles Edwin Webster; Joel T Mague; Russell H Schmehl; James P Donahue

doi:10.1021/acs.inorgchem.9b02252

Photocatalytic H₂-Evolution by Homogeneous Molybdenum Sulfide Clusters Supported by Dithiocarbamate Ligands

Inorg Chem. 2019 Dec 16;58(24):16458-16474. doi: 10.1021/acs.inorgchem.9b02252. Epub 2019 Dec 2.

Affiliations

¹ Department of Chemistry , Tulane University , 6400 Freret Street , New Orleans , Louisiana 70118-5698 , United States.
² Department of Chemistry and Biochemistry , University of Mississippi , Oxford , Mississippi 38655 , United States.
³ Department of Chemistry , Mississippi State University , P.O. Box 9573, Mississippi State , Mississippi 39762-9573 , United States.

PMID: 31790221
DOI: 10.1021/acs.inorgchem.9b02252

Abstract

Irradiation at 460 nm of [Mo₃(μ₃-S)(μ₂-S₂)₃(S₂CNR₂)₃]I ([2a]I, R = Me; [2b]I, R = Et; [2c]I, R = ⁱBu; [2d]I, R = CH₂C₆H₅) in a mixed aqueous-polar organic medium with [Ru(bipy)₃]²⁺ as photosensitizer and Et₃N as electron donor leads to H₂ evolution. Maximum activity (300 turnovers, 3 h) is found with R = ⁱBu in 1:9 H₂O:MeCN; diminished activity is attributed to deterioration of [Ru(bipy)₃]²⁺. Monitoring of the photolysis mixture by mass spectrometry suggests transformation of [Mo₃(μ₃-S)(μ₂-S₂)₃(S₂CNR₂)₃]⁺ to [Mo₃(μ₃-S)(μ₂-S)₃(S₂CNR₂)₃]⁺ via extrusion of sulfur on a time scale of minutes without accumulation of the intermediate [Mo₃S₆(S₂CNR₂)₃]⁺ or [Mo₃S₅(S₂CNR₂)₃]⁺ species. Deliberate preparation of [Mo₃S₄(S₂CNEt₂)₃]⁺ ([3]⁺) and treatment with Et₂NCS₂^1- yields [Mo₃S₄(S₂CNEt₂)₄] (4), where the fourth dithiocarbamate ligand bridges one edge of the Mo₃ triangle. Photolysis of 4 leads to H₂ evolution but at ∼25% the level observed for [Mo₃S₇(S₂CNEt₂)₃]⁺. Early time monitoring of the photolyses shows that [Mo₃S₄(S₂CNEt₂)₄] evolves H₂ immediately and at constant rate, while [Mo₃S₇(S₂CNEt₂)₃]⁺ shows a distinctive incubation prior to a more rapid H₂ evolution rate. This observation implies the operation of catalysts of different identity in the two cases. Photolysis solutions of [Mo₃S₇(S₂CNⁱBu₂)₃]⁺ left undisturbed over 24 h deposit the asymmetric Mo₆ cluster [(ⁱBu₂NCS₂)₃(μ₂-S₂)₂(μ₃-S)Mo₃](μ₃-S)(μ₃-η²,η¹-S',η¹-S″-S₂)[Mo₃(μ₂-S)₃(μ₃-S)(S₂CNⁱBu₂)₂(μ₂-S₂CNⁱBu₂)] in crystalline form, suggesting that species with this hexametallic composition and core topology are the probable H₂-evolving catalysts in photolyses beginning with [Mo₃S₇(S₂CNR₂)₃]⁺. When used as solvent, N,N-dimethylformamide (DMF) suppresses H₂-evolution but to a greater degree for [Mo₃S₄(S₂CNEt₂)₄] than for [Mo₃S₇(S₂CNEt₂)₃]⁺. Recrystallization of [Mo₃S₄(S₂CNEt₂)₄] from DMF affords [Mo₃S₄(S₂CNEt₂)₄(η¹,κO-DMF)] (5), implying that inhibition by DMF arises from competition for a Mo coordination site that is requisite for H₂ evolution. Computational assessment of [Mo₃S₄(S₂CNMe₂)₃]⁺ following addition of 2H⁺ and 2e^- suggests a Mo(H)-μ₂(SH) intermediate as the lowest energy species for H₂ elimination. An analogous pathway may be available to the Mo₆ cluster via dissociation of one end of the μ₂-S₂CNR₂ ligand, a known hemilabile ligand type, in the [Mo₃S₄]⁴⁺ fragment.