Please use this identifier to cite or link to this item: https://scholarbank.nus.edu.sg/handle/10635/92887
DC FieldValue
dc.title[Pt2(PPh3)4(μ-S)2] as a metalloligand toward main-group Lewis acids: Theoretical study of intermetallic complexes with T1(I), Pb(II), In(III) and Ga(III)
dc.contributor.authorTan, A.L.
dc.contributor.authorChiew, M.L.
dc.contributor.authorHor, T.S.A.
dc.date.accessioned2014-10-16T08:17:56Z
dc.date.available2014-10-16T08:17:56Z
dc.date.issued1997-04-21
dc.identifier.citationTan, A.L.,Chiew, M.L.,Hor, T.S.A. (1997-04-21). [Pt2(PPh3)4(μ-S)2] as a metalloligand toward main-group Lewis acids: Theoretical study of intermetallic complexes with T1(I), Pb(II), In(III) and Ga(III). Journal of Molecular Structure: THEOCHEM 393 (1-3 SPEC. ISS.) : 189-196. ScholarBank@NUS Repository.
dc.identifier.issn01661280
dc.identifier.urihttp://scholarbank.nus.edu.sg/handle/10635/92887
dc.description.abstractThis paper describes theoretical studies on adducts of Pt2(PPh3)4(μ-S)2 with Tl(I), Pb(II), In(III) and Ga(III). Using one of the Pb compounds as an example, the fundamental principle of competition for interactions (M-ligand vs. M-S; M-S vs. Pt-S) is illustrated; in particular, any ligand bound trans to an M-S bond will cause the latter to be weakened more than the other M-S bond. The polarizable phosphine ligands also play a role in moderating changes in the Pt-S interactions. The general weakening of the M-S bonds upon ligand coordination, which is also demonstrated by binding energies of Pt2(PPh3)4(μ-S)2 to various heterometal fragments, could explain why Ga, Pb and Tl do not accept additional ligands. In (PPh3)4Pt2(μ2-S) 2InCl3, the In atom is square pyramidally coordinated. Calculations indicate strong pπ-pπ and dπ-pπ bonding between In and the Cl atom at the apex of the square pyramid, thus accounting for the unusually short In-Cl bond length. With regard to the trend of increasing Pt-S-S-Pt dihedral angle with increasing heterometal size, it is found that in the parent compound (without the heterometal M), the dihedral angle determines the character of the sulfur lone pairs; it is inferred that the "optimal" orientation of the lone pairs for interactions with the heterometal depends on the size of the latter. This result has implications for all binuclear Pt(II) or Pd(II) compounds with bridging sulfur ligand(s). © 1997 Elsevier Science B.V. All rights reserved.
dc.sourceScopus
dc.subjectFenske-hall calculations
dc.subjectIntermetallic
dc.subjectMetalloligand
dc.subjectPlatinum
dc.subjectSulfur
dc.typeArticle
dc.contributor.departmentCHEMISTRY
dc.contributor.departmentCOMPUTATIONAL SCIENCE
dc.description.sourcetitleJournal of Molecular Structure: THEOCHEM
dc.description.volume393
dc.description.issue1-3 SPEC. ISS.
dc.description.page189-196
dc.description.codenTHEOD
dc.identifier.isiutNOT_IN_WOS
Appears in Collections:Staff Publications

Show simple item record
Files in This Item:
There are no files associated with this item.

Page view(s)

63
checked on Mar 29, 2020

Google ScholarTM

Check


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.