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Article: From aggregates to clusters. Facile formation of hetero-metal-metal bonds through reductive desulfurization by CO in a decapacitative transformation of a {Pt2MS2} Tbp frame to a {Pt2MS} tetrahedral core (M = Ag, Cu, and Ru)

TitleFrom aggregates to clusters. Facile formation of hetero-metal-metal bonds through reductive desulfurization by CO in a decapacitative transformation of a {Pt<inf>2</inf>MS<inf>2</inf>} Tbp frame to a {Pt<inf>2</inf>MS} tetrahedral core (M = Ag, Cu, and Ru)
Authors
Issue Date1997
Citation
Journal of the American Chemical Society, 1997, v. 119, n. 45, p. 11006-11011 How to Cite?
Abstract[Pt2(PPh3)4(μ-S2] (1) reacts with AgCl(PPH3) and CuCl under a mild pressure of CO (60 psi) to give [Pt2(CO)(PPh3)3(μ3-S)MCl] [M = Ag (4) and Cu (6)] via the intermediates [Pt2(PPh3))4(μ3-S)2Ag(PPh3)]Cl (2a), [Pt2(PPh3)5(μ3-S)2CuCl] (5), respectively. These transformations demonstrate an precedented concomitant process which involve heterometalation, carbonylation, reductive desulfurization, and metal-metal bond formation. The Ru-Pt aggregate of [Pt2(PPh3)4(μ3-S)2(RuCl(PPh3)2]Cl (7), prepared from 1 and RuCl2(PPh3)3, similarly converts to a [Pt2(CO2(PPh3)2(PPh3)2(μ3-S)RuCl(CO)(PPh3)]Cl (8) cluster under a CO atmosphere. Such transformation establishes a synthetic relationship between the {Pt2MS2} trigonal bipyramidal aggregates and {Pt2MS} tetrahedral clusters and provides a general entry to triangular heterometallic sulfide clusters of platinum. All complexes are characterized by IR, 31P{1H}, and 13C NMR spectroscopy and conductivity measurements. The structures of 4, 6, and the PF6- derivative of 2a (viz. 2b) have also determined by single-crystal X-ray diffraction analyses. The structure of 2b shows a sulfide-bicapped Ag-Pt mixed-metal triangle without significant Pt···Pt [3.351(2) and 3.375(2) Å] or Ag···Pt [av 3.064(1) and 3.101(1) Å] interactions. Complex 2b crystallizes in two polymorphic modifications with different degrees of disposition of the Ag moieties with respect to the {Pt2S2} core. As a result, the Ag-S bonds [2.479(1) vs 2.585(1) Å and 2.502(2) vs 2.607(2) Å] are significantly different between the polymorphs in which the Ag···Pt distances are near-equivalent[3.061(1) Å] in one form but significantly different [2.9621(1) vs 3.240(1) Å] in the other. Complex 4 shows a triangular {AgPt2} cluster mono-capped by sulfide. Removal of a capping sulfur atom from 2a effectively reduces both Pt(II) centers and favors Pt-Pt bond formation [Pt-Pt 2.658(2) Å] and heterometallic Ag-Pt interactions [av Ag-Pt 2.965(1) Å in 4. Both the Pt-S and Ag-S bonds also strengthen significantly from 2b to 4. Cluster 6 is isostructural to 4 with similar homo-[Pt-Pt 2.657(1) Å] and heterometal [av Cu-Pt 2.832(1) Å interactions. Both 4 and 6 thus constitute a {MPt2S} distorted tetrahedral cluster frame. A facile and general aggregates-to clusters conversion through the elimination of COS gas is thus established.
Persistent Identifierhttp://hdl.handle.net/10722/237551
ISSN
2020 Impact Factor: 15.419
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLiu, Huang-
dc.contributor.authorTan, Agnes L.-
dc.contributor.authorMok, K. F.-
dc.contributor.authorMak, Thomas C W-
dc.contributor.authorBatsanov, Andrei S.-
dc.contributor.authorHoward, Judith A K-
dc.contributor.authorAndy Hor, T. S.-
dc.date.accessioned2017-01-16T06:09:41Z-
dc.date.available2017-01-16T06:09:41Z-
dc.date.issued1997-
dc.identifier.citationJournal of the American Chemical Society, 1997, v. 119, n. 45, p. 11006-11011-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/237551-
dc.description.abstract[Pt2(PPh3)4(μ-S2] (1) reacts with AgCl(PPH3) and CuCl under a mild pressure of CO (60 psi) to give [Pt2(CO)(PPh3)3(μ3-S)MCl] [M = Ag (4) and Cu (6)] via the intermediates [Pt2(PPh3))4(μ3-S)2Ag(PPh3)]Cl (2a), [Pt2(PPh3)5(μ3-S)2CuCl] (5), respectively. These transformations demonstrate an precedented concomitant process which involve heterometalation, carbonylation, reductive desulfurization, and metal-metal bond formation. The Ru-Pt aggregate of [Pt2(PPh3)4(μ3-S)2(RuCl(PPh3)2]Cl (7), prepared from 1 and RuCl2(PPh3)3, similarly converts to a [Pt2(CO2(PPh3)2(PPh3)2(μ3-S)RuCl(CO)(PPh3)]Cl (8) cluster under a CO atmosphere. Such transformation establishes a synthetic relationship between the {Pt2MS2} trigonal bipyramidal aggregates and {Pt2MS} tetrahedral clusters and provides a general entry to triangular heterometallic sulfide clusters of platinum. All complexes are characterized by IR, 31P{1H}, and 13C NMR spectroscopy and conductivity measurements. The structures of 4, 6, and the PF6- derivative of 2a (viz. 2b) have also determined by single-crystal X-ray diffraction analyses. The structure of 2b shows a sulfide-bicapped Ag-Pt mixed-metal triangle without significant Pt···Pt [3.351(2) and 3.375(2) Å] or Ag···Pt [av 3.064(1) and 3.101(1) Å] interactions. Complex 2b crystallizes in two polymorphic modifications with different degrees of disposition of the Ag moieties with respect to the {Pt2S2} core. As a result, the Ag-S bonds [2.479(1) vs 2.585(1) Å and 2.502(2) vs 2.607(2) Å] are significantly different between the polymorphs in which the Ag···Pt distances are near-equivalent[3.061(1) Å] in one form but significantly different [2.9621(1) vs 3.240(1) Å] in the other. Complex 4 shows a triangular {AgPt2} cluster mono-capped by sulfide. Removal of a capping sulfur atom from 2a effectively reduces both Pt(II) centers and favors Pt-Pt bond formation [Pt-Pt 2.658(2) Å] and heterometallic Ag-Pt interactions [av Ag-Pt 2.965(1) Å in 4. Both the Pt-S and Ag-S bonds also strengthen significantly from 2b to 4. Cluster 6 is isostructural to 4 with similar homo-[Pt-Pt 2.657(1) Å] and heterometal [av Cu-Pt 2.832(1) Å interactions. Both 4 and 6 thus constitute a {MPt2S} distorted tetrahedral cluster frame. A facile and general aggregates-to clusters conversion through the elimination of COS gas is thus established.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleFrom aggregates to clusters. Facile formation of hetero-metal-metal bonds through reductive desulfurization by CO in a decapacitative transformation of a {Pt<inf>2</inf>MS<inf>2</inf>} Tbp frame to a {Pt<inf>2</inf>MS} tetrahedral core (M = Ag, Cu, and Ru)-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja9718376-
dc.identifier.scopuseid_2-s2.0-0030688954-
dc.identifier.volume119-
dc.identifier.issue45-
dc.identifier.spage11006-
dc.identifier.epage11011-
dc.identifier.isiWOS:A1997YG27300016-
dc.identifier.issnl0002-7863-

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