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Reactivity of the phosphinito bridged Pt(i) complex [(PHCy(2))Pt(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(PHCy(2))](Pt-Pt) towards Au(i) and Ag(i) electrophiles.
MedLine Citation:
PMID:  23212558     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The reactivity of the phosphinito bridged Pt(i) complex [(PHCy(2))Pt(1)(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(2)(PHCy(2))](Pt-Pt) () towards Au(i) and Ag(i) electrophiles was explored. Treatment of with AuCl yielded the dichloro Pt(ii) complex [(Cl)(PHCy(2))Pt(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(Cl)(PHCy(2))] (), while [Au(PPh(3))Cl] in thf (or toluene) caused ligand exchange resulting in the formation of [(PPh(3))Pt(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(PHCy(2))](Pt-Pt) () and [(PPh(3))Pt(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(PPh(3))](Pt-Pt) (). With [Au(PPh(3))OTf] (independently from the solvent) or with [Au(PPh(3))Cl] (only in dichloromethane), reaction with gave [(PHCy(2))Pt(1)(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(2){μ-Au(PPh(3))}(PHCy(2))]X(Pt-Pt) ([]X, X = OTf, Cl) clusters in which the [Au(PPh(3))] moiety bridges the μP-Pt(2) bond. The [Ag(PPh(3))](+) electrophile attacks complex selectively at the Pt(2)-μP bond to afford, at low T, the cationic cluster [(PHCy(2))Pt(1)(μ-PCy(2)){κ(2)P,O-μ-P(O)Cy(2)}Pt(2){μ-Ag(PPh(3))}(PHCy(2))](+)(Pt-Pt) () in which the [Ag(PPh(3))](+) moiety bridges the μP-Pt(2) bond. Clusters analogous to , but without PPh(3) bonded to Ag, are obtained from reactions of with AgOTf, AgBF(4), AgClO(4) and AgCl.
Authors:
Mario Latronico; Sergio Sánchez; Antonino Rizzuti; Vito Gallo; Flavia Polini; Elena Lalinde; Piero Mastrorilli
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-12-4
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Dec 
Date Detail:
Created Date:  2012-12-5     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh), Politecnico di Bari, via Orabona 4, I-70125 Bari, Italy. p.mastrorilli@poliba.it.
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