Unique reactivity characteristics of Mo-coordinated S2-2 and S2-4 ligands
dc.contributor.author | Coucouvanis, Dimitri | en_US |
dc.contributor.author | Hadjikyriacou, A. | en_US |
dc.contributor.author | Draganjac, M. | en_US |
dc.contributor.author | Kanatzidis, Mercouri G. | en_US |
dc.contributor.author | Ileperuma, O. | en_US |
dc.date.accessioned | 2006-04-07T19:39:23Z | |
dc.date.available | 2006-04-07T19:39:23Z | |
dc.date.issued | 1986 | en_US |
dc.identifier.citation | Coucouvanis, D., Hadjikyriacou, A., Draganjac, M., Kanatzidis, M. G., Ileperuma, O. (1986)."Unique reactivity characteristics of Mo-coordinated S2-2 and S2-4 ligands." Polyhedron 5(1-2): 349-356. <http://hdl.handle.net/2027.42/26402> | en_US |
dc.identifier.uri | http://www.sciencedirect.com/science/article/B6TH8-430XDT8-20/2/ef62f9e75a87db517ae9695c26b4d099 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/26402 | |
dc.description.abstract | The synthesis of the new dithiolene complexes, [{(MeOOC)2C2S2}2Mo([mu]2-S)]-2 and [OMo(S2C2(COOMe)2)2]-, is reported. These complexes are obtained by the reaction of dicarbomethoxyacetylene (DMA) with either [(S4)Mo(S)([mu]2-S)2Mo(S)(S4)]2- or [(CS4)Mo(S)([mu]2-S)2Mo(S)(CS4)]2- and [OMo(S4)2]2-, respectively. The reaction of [(S4)Mo(O)([mu]2-S)2Mo(O)(S2)]2- with DMA results in the new dithiolene complex [{(MeOOC)2C2S2}Mo(O)([mu]2-S)]-2, which is the isomeric form of the vinyl disulfide complex obtained in the reaction of the [(S2)Mo(O)([mu]2-S)2Mo(O)(S2)]2- complex with DMA. The difference in reactivity between the two complexes that contain the same [Mo2O2S2]2+ core is attributed to the intrinsically different reactivity characteristics of the S2-4 and S2-2 ligands. As a result of Mo-S d[pi]-p[pi] bonding an alternation in the S---S bond lengths is observed in virtually all of the structurally characterized Mo-S4 units. The consequent weakening of the S---S bonds adjacent to the Mo---S bonds allows for the ready dissociation of S02 from the Mo-coordinated S2-4 ligands. This weakening also accounts for the facile formation of dithiolenes in cycloaddition reactions of alkynes with the Mo-S4 units. By comparison, the S---S bond in side-on Mo-coordinated S2-2 ligands is strengthened as a result of depopulation of the ligand [pi]*-orbitals. Reactions of the latter with alkynes do not proceed by cycloaddition. Instead, insertion into the Mo---O bond has been reported for at least one such reaction. The importance of activated polysulfide ligands in the hydrodesulfurization reaction is discussed. | en_US |
dc.format.extent | 689278 bytes | |
dc.format.extent | 3118 bytes | |
dc.format.mimetype | application/pdf | |
dc.format.mimetype | text/plain | |
dc.language.iso | en_US | |
dc.publisher | Elsevier | en_US |
dc.title | Unique reactivity characteristics of Mo-coordinated S2-2 and S2-4 ligands | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Materials Science and Engineering | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbsecondlevel | Chemical Engineering | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.subject.hlbtoplevel | Engineering | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A. | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A. | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A. | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A. | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A. | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/26402/1/0000489.pdf | en_US |
dc.identifier.doi | http://dx.doi.org/10.1016/S0277-5387(00)84932-3 | en_US |
dc.identifier.source | Polyhedron | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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