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Pt-M (M = Au and Tl) Dative Bonds Using Bis(cyclometalated)platinum(II) Complexes

Rajabi, S ; Sharif University of Technology | 2019

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  1. Type of Document: Article
  2. DOI: 10.1021/acs.organomet.8b00907
  3. Publisher: American Chemical Society , 2019
  4. Abstract:
  5. Symmetrical and unsymmetrical biscyclometalated platinum(II) complexes [Pt(ptpy)2], 1, and [Pt(ptpy)(bppy)], 2, in which ptpy = deprotonated 2-(p-tolyl)pyridine and bppy = deprotonated 2-(3-bromophenyl)pyridine, have been prepared from the reaction between tris(pentafluorophenyl)borane, B(C6F5)3 and 1 equiv of monocyclometalated complexes [PtMe(ptpy)(ptpyH)], B, and [PtMe(ptpy)(bppyH)], C, respectively. The solid-state structures of 1 and 2 have been determined by X-ray crystallography. The reaction of 1 with 1 equiv of TlPF6 or [Au(PPh3)]OTF resulted in the production of heteronuclear complexes [Pt(ptpy)2Tl]PF6, 3 and {Pt(ptpy)2[Au(PPh3)]}OTF, 4, respectively. X-ray diffraction data showed that in solid state, complex 4 exists as a mixture of supported and unsupported PtII-AuI-bonded structures, whereas complex 3 consists of an infinite helical chain structure built up by unsupported Pt-Tl dative bonds. Absorption, emission, and NMR spectroscopy data showed that both Pt-Tl and Pt-Au bonds in 3 and 4 have dynamic behavior. The low-temperature 1H, 31P{1H}, and exchange spectroscopy NMR of 4 revealed two dynamic behaviors involving the rupture of the Au-Cipso bond as well as the dissociation-association of the [Au(PPh3)]+ and Pt(ptpy)2 fragments. All complexes displayed bright emission in the solid state, and their absorption and emission properties have been investigated both experimentally and by time-dependent density functional theory calculations
  6. Keywords:
  7. Binary alloys ; Density functional theory ; Gold ; Nuclear magnetic resonance spectroscopy ; Phosphorus compounds ; Platinum alloys ; Pyridine ; Temperature ; X ray crystallography ; Absorption and emissions ; Exchange spectroscopies ; Helical chain structure ; Heteronuclear complexes ; Solid-state structures ; Time dependent density functional theory calculations ; Tris(pentafluorophenyl) borane ; X-ray diffraction data ; Platinum compounds
  8. Source: Organometallics ; Volume 38, Issue 8 , 2019 , Pages 1709-1720 ; 02767333 (ISSN)
  9. URL: https://pubs.acs.org/doi/10.1021/acs.organomet.8b00907