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Reaction of H2S with MoRu(CO)(6)(dppm)(2) to give H-2 and a bridged-sulfide product via hydrido-sulfhydryl intermediates (dppm = Ph2PCH2PPh2)

TitleReaction of H2S with MoRu(CO)(6)(dppm)(2) to give H-2 and a bridged-sulfide product via hydrido-sulfhydryl intermediates (dppm = Ph2PCH2PPh2)
Publication TypeJournal Article
Year of Publication2006
AuthorsKhorasani-Motlagh, M, Safari, N, Pamplin, CB, Patrick, BO, James, BR
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume84
Pagination330-336
Date PublishedFeb
Type of ArticleArticle
ISBN Number0008-4042
Keywordsbis(diphenylphosphino) methane, bis(diphenylphosphino)methane, BOND ACTIVATION, bridged-sulfide complex, carbonyl complexes, CHEMISTRY, COMPLEXES, hydrido-sulfhydryl species, HYDROGEN, HYDROGEN-SULFIDE, MECHANISTIC ASPECTS, METAL, MO, MOLYBDENUM, RECOVERY, ruthenium, sulfide, SULFUR-DIOXIDE
Abstract

Oxidative addition of H2S to MoRu(CO)(6)(mu-dppm)(2) (1) at similar to 20 degrees C in toluene yields an isolable complex formulated as Mo(CO)(3)(mu-SH)(mu-CO)(mu-dppm)(2)RuH(CO) (2) via the possible intermediate Mo(CO)(3)(mu-H)(mu-CO)(mu-dppm)(2)Ru(SH)(CO) (4) (dppm = Ph2PCH2PPh2) that is detectable at lower temperatures. Over 2 days, species 2 in toluene loses H-2 (and CO) to yield the bridged-sulfide product, Mo(CO)(2)(mu-CO)(mu-S)(mu-dppm)(2)Ru(CO) (5) that is also formed directly from the reaction of 1 with elemental sulfur. The solid-state molecular structure of 5 is determined by X-ray crystallography. A further hydrido-sulfhydryl species, possibly Mo(CO)(3)(mu-SH)(mu-H)(mu-dppm)(2)Ru(CO)(2) (3), is in equilibrium with 2 at ambient temperature.

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