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

Paul Raithby, Sheida Rajabi, Sirous Jamali, Soroosh Naseri, Ali Jamiah, Reza Kia, Hamidreza Samouei, Piero Mastrorilli, Hamid Shahsavari

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Abstract

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(C 6 F 5 ) 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 TlPF 6 or [Au(PPh 3 )]OTF resulted in the production of heteronuclear complexes [Pt(ptpy) 2 Tl]PF 6 , 3 and {Pt(ptpy) 2 [Au(PPh 3 )]}OTF, 4, respectively. X-ray diffraction data showed that in solid state, complex 4 exists as a mixture of supported and unsupported Pt II -Au I -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 1 H, 31 P{ 1 H}, and exchange spectroscopy NMR of 4 revealed two dynamic behaviors involving the rupture of the Au-C ipso bond as well as the dissociation-association of the [Au(PPh 3 )] + 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.

Original languageEnglish
Pages (from-to)1709-1720
Number of pages12
JournalOrganometallics
Volume38
Issue number8
Early online date8 Apr 2019
DOIs
Publication statusPublished - 22 Apr 2019

Keywords

  • platinum
  • Gold
  • Thallium
  • Dative bonds
  • Crystallography
  • Cyclometallation

ASJC Scopus subject areas

  • Chemistry(all)

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    Raithby, P., Rajabi, S., Jamali, S., Naseri, S., Jamiah, A., Kia, R., Samouei, H., Mastrorilli, P., & Shahsavari, H. (2019). Pt-M (M = Au and Tl) Dative Bonds Using Bis(cyclometalated)platinum(II) Complexes. Organometallics, 38(8), 1709-1720. https://doi.org/10.1021/acs.organomet.8b00907