Opin vísindi

Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide

Show simple item record

dc.contributor Háskóli Íslands
dc.contributor University of Iceland
dc.contributor.author Birgisson, Benedikt Orri
dc.contributor.author Monger, Lindsey J.
dc.contributor.author Damodaran, Krishna Kumar
dc.contributor.author Suman, Sigridur G
dc.date.accessioned 2020-08-10T13:42:11Z
dc.date.available 2020-08-10T13:42:11Z
dc.date.issued 2020-02
dc.identifier.citation Birgisson, B. O., Monger, L. J., Damodaran, K. K., & Suman, S. G. (2020). Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide. Inorganica Chimica Acta, 501, 119272. doi:https://doi.org/10.1016/j.ica.2019.119272
dc.identifier.issn 0020-1693
dc.identifier.uri https://hdl.handle.net/20.500.11815/1951
dc.description Post-print (lokagerð höfundar)
dc.description.abstract Crystalline and amorphous molybdenum sulfide “MoSx” catalysts are well established in sulfur removal from petrochemicals in heterogeneous reactions. Accessibility of sulfido ligands on the catalyst surface is generally accepted as pre-requisite for catalytic initiation. Interest in study of discrete molecules with similar active sites for sulfur transfer reactions in organic reactions prompted synthesis of the asymmetric dinuclear complexes, [Mo2O2(μ-S)2(S2)(L)] (1, L = bipyridine (bipy); 2, L = ethylene diamine (en), 3, L = diethylenediamine (dien)) in facile ligand exchange reaction. A single crystal of 1 was obtained from DMF/ether solution as dark red plates and analyzed by X-ray diffraction. The complexes remove sulfur from propylene sulfide in a heterogeneous reaction at ambient temperature on the NMR scale. Reactivity expected to reflect the donation properties of L with the largest LMCT contribution rendering the most reactive sulfido ligand yielded surprising results. DFT calculations of the optimized minimal energy structures of all three complexes were performed and several possible isomeric structures evaluated. The optimal energy form of 1 compared well with its crystal structure and results from calculated structures of 2 and 3 agree with spectroscopic observations. The modest reactivity is in agreement with poor access to the disulfide as inferred by DFT structures of the complexes and the crystal structure of 1 where strong SS interactions were found along its b-axis.
dc.description.sponsorship Icelandic Centre for Research (173667)
dc.format.extent 119272
dc.language.iso en
dc.publisher Elsevier BV
dc.relation.ispartofseries Inorganica Chimica Acta;501(11)
dc.rights info:eu-repo/semantics/embargoedAccess
dc.subject Propylen
dc.subject Sulfide
dc.subject Molybdenum
dc.subject Sulfur abstraction
dc.subject Kristallar
dc.subject Brennisteinn
dc.subject Mólýbden
dc.subject Frumefni
dc.subject Efnasambönd
dc.title Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide
dc.type info:eu-repo/semantics/article
dc.description.version Peer reviewed
dc.identifier.journal Inorganica Chimica Acta
dc.identifier.doi 10.1016/j.ica.2019.119272
dc.contributor.department Raunvísindastofnun (HÍ)
dc.contributor.department Science Institute (UI)
dc.contributor.department Raunvísindadeild (HÍ)
dc.contributor.department Faculty of Physical Sciences (UI)
dc.contributor.school Verkfræði- og náttúruvísindasvið (HÍ)
dc.contributor.school School of Engineering and Natural Sciences (UI)

Files in this item

This item appears in the following Collection(s)

Show simple item record