dc.contributor.author | Konu, Jari | |
dc.contributor.author | Chivers, Tristram | |
dc.contributor.author | Tuononen, Heikki | |
dc.date.accessioned | 2015-11-25T08:06:23Z | |
dc.date.available | 2015-11-25T08:06:23Z | |
dc.date.issued | 2011 | |
dc.identifier.citation | Konu, J., Chivers, T., & Tuononen, H. (2011). Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh2P)2CEEC(PPh2S)2]2− (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S). <i>Chemistry - A European Journal</i>, <i>17</i>(42), 11844-11856. <a href="https://doi.org/10.1002/chem.201100891" target="_blank">https://doi.org/10.1002/chem.201100891</a> | |
dc.identifier.other | CONVID_20998498 | |
dc.identifier.other | TUTKAID_48998 | |
dc.identifier.uri | https://jyx.jyu.fi/handle/123456789/47816 | |
dc.description.abstract | The metathetical reactions of a) [Li(tmeda)]2[(S)C(PPh2S)2] (Li2⋅3 c) with CuCl2 and b) [Li(tmeda)]2[(SPh2P)2CSSC(PPh2S)2] (Li2⋅4 c) with two equivalents of CuCl both afford the binuclear CuI complex {Cu2[(SPh2P)2CSSC(PPh2S)2]} (5 c). The elongated (C)S[BOND]S(C) bond (ca. 2.54 and 2.72 Å) of the dianionic ligand observed in the solid-state structure of 5 c indicate the presence of diradical character as supported by theoretical analyses. The treatment of [Li(tmeda)]2[(SPh2P)2CSeSeC(PPh2S)2] (Li2⋅4 b) and Li2⋅4 c with AgOSO2CF3 produce the analogous AgI derivatives, {Ag2[(SPh2P)2CEEC(PPh2S)2]} (6 b, E=Se; 6 c, E=S), respectively. The diselenide complex 6 b exhibits notably weaker Ag[BOND]Se(C) bonds than the corresponding contacts in the CuI congeners, and the 31P NMR data suggest a possible isomerization in solution. In contrast to the metathesis observed for CuI and AgI reagents, the reactions of Li2⋅4 b and Li2⋅4 c with Au(CO)Cl involve a redox process in which the dimeric dichalcogenide ligands are reduced to the corresponding monomeric dianions, [(E)C(PPh2S)2]2− (3 b, E=Se; 3 c, E=S), and one of the gold centers is oxidized to generate the mixed-valent AuI/AuIII complexes, {Au[(E)C(PPh2S)2]}2 (7 b, E=Se; 7 c, E=S), with relatively strong aurophilic AuI⋅⋅⋅AuIII interactions. The new compounds 5 c, 6 b,c and 7 b,c are characterized in solution by NMR spectroscopy and in the solid state by X-ray crystallography (5 c, 6 b, 7 b and 7 c) and by Raman spectroscopy (5 c and 6 c). The UV-visible spectra of coinage metal complexes of the type 5, 6 and 7 are discussed in the light of results from theoretical analyses using time-dependent density functional theory. | |
dc.language.iso | eng | |
dc.publisher | Wiley | |
dc.relation.ispartofseries | Chemistry - A European Journal | |
dc.subject.other | ryhmän 11 metallit | |
dc.subject.other | dikalkogenidit | |
dc.subject.other | diradikaaliluonne | |
dc.subject.other | elektronirakenne | |
dc.subject.other | hapetus-pelkistys-kemia | |
dc.subject.other | coinage metals | |
dc.subject.other | dichalcogenides | |
dc.subject.other | diradical character | |
dc.subject.other | electronic structure | |
dc.subject.other | redox chemistry | |
dc.title | Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh2P)2CEEC(PPh2S)2]2− (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S) | |
dc.type | article | |
dc.identifier.urn | URN:NBN:fi:jyu-201511243776 | |
dc.contributor.laitos | Kemian laitos | fi |
dc.contributor.laitos | Department of Chemistry | en |
dc.contributor.oppiaine | Epäorgaaninen ja analyyttinen kemia | fi |
dc.contributor.oppiaine | Inorganic and Analytical Chemistry | en |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | |
dc.date.updated | 2015-11-24T07:15:16Z | |
dc.type.coar | http://purl.org/coar/resource_type/c_2df8fbb1 | |
dc.description.reviewstatus | peerReviewed | |
dc.format.pagerange | 11844-11856 | |
dc.relation.issn | 0947-6539 | |
dc.relation.numberinseries | 42 | |
dc.relation.volume | 17 | |
dc.type.version | acceptedVersion | |
dc.rights.copyright | © 2011 Wiley-VCH Verlag GmbH & Co.This is a final draft version of an article whose final and definitive form has been published by WIley. Published in this repository with the kind permission of the publisher. | |
dc.rights.accesslevel | openAccess | fi |
dc.relation.doi | 10.1002/chem.201100891 | |
dc.type.okm | A1 | |