Loading...

A cooperative pathway for water activation using a bimetallic Pt0-CuI system

Jamali, S ; Sharif University of Technology | 2016

1351 Viewed
  1. Type of Document: Article
  2. DOI: 10.1039/c6dt03305a
  3. Publisher: Royal Society of Chemistry , 2016
  4. Abstract:
  5. A mixture of the platinum(0) complex [Pt(PtBu3)2] and tetrakis(acetonitrile)copper(i) hexafluorophosphate in acetone activated a water molecule and gave the hydride platinum(ii) complex [PtH(CH3CN)(PtBu3)2]PF6, 1, and the hydroxide Cu(i) species. The crystal structure of complex 1 was determined by X-ray crystallography, indicating a distorted square planar geometry around the platinum center. Although three possible mechanisms are proposed for this transformation, monitoring of the reaction using NMR spectroscopy at low temperature reveals that a cooperative pathway involving formation of a Pt0-CuI dative bond complex is the most probable pathway. The hydride platinum complex 1 is stable in acidic and neutral conditions but undergoes intramolecular C-H activation in the presence of pyridine. Monitoring of the reaction using 1H and 31P NMR spectroscopy shows that a cyclometalation reaction of one of the phosphine ligands is followed by displacement of a second phosphine ligand by pyridine to give the cyclometalated platinum(ii) complex, [Pt(κ2 PC-PtBu2CMe2CH2)(py)2], 4. The structure of 4 in solution and solid state phases was determined using NMR spectroscopy and X-ray crystallography, respectively
  6. Keywords:
  7. Acetone ; Activation analysis ; Chemical activation ; Copper compounds ; Crystal structure ; Crystallography ; Geometry ; Hydrides ; Ligands ; Molecules ; Nuclear magnetic resonance spectroscopy ; Phosphorus compounds ; Platinum ; Pyridine ; Self assembly ; Temperature ; 31P-NMR spectroscopy ; Hexafluorophosphates ; Intramolecular C-H activation ; Neutral conditions ; Platinum(0) complexes ; Possible mechanisms ; Solid-state phasis ; Square planar geometry ; X- ray crystallography
  8. Source: Dalton Transactions ; Volume 45, Issue 44 , 2016 , Pages 17644-17651 ; 14779226 (ISSN)
  9. URL: http://pubs.rsc.org/en/Content/ArticleLanding/2016/DT/C6DT03305A#!divAbstract