Phosphine and Selenoether peri-Substituted Acenaphthenes and Their Transition-Metal Complexes: Structural and NMR Investigations: Inorganic Chemistry

Lutao Zhang, F.A. Christie, A.E. Tarcza, H.G. Lancaster, L.J. Taylor, M. Bühl, O.L. Malkina, J.D. Woollins, C.L. Carpenter-Warren, D.B. Cordes, A.M.Z. Slawin, B.A. Chalmers, P. Kilian

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

A series of peri-substituted acenaphthene-based phosphine selenoether bidentate ligands Acenap(iPr2P)(SeAr) (L1-L4, Acenap = acenaphthene-5,6-diyl, Ar = Ph, mesityl, 2,4,6-trisopropylphenyl and supermesityl) were prepared. The rigid acenaphthene framework induces a forced overlap of the phosphine and selenoether lone pairs, resulting in a large magnitude of through-space 4JPSe coupling, ranging from 452 to 545 Hz. These rigid ligands L1-L4 were used to prepare a series of selected late d-block metals, mercury, and borane complexes, which were characterized, including by multinuclear NMR and single-crystal X-ray diffraction. The Lewis acidic motifs (BH3, Mo(CO)4, Ag+, PdCl2, PtCl2, and HgCl2) bridge the two donor atoms (P and Se) in all but one case in the solid-state structures. Where the bridging motif contained NMR-active nuclei (11B, 107Ag, 109Ag, 195Pt, and 199Hg), JPM and JSeM couplings are observed directly, in addition to the altered JPSe in the respective NMR spectra. The solution NMR data are correlated with single-crystal diffraction data, and in the case of mercury(II) complexes, they are also correlated with the solid-state NMR data and coupling deformation density calculations. The latter indicate that the through-space interaction dominates in free L1, while in the L1HgCl2 complex, the main coupling pathway is via the metal atom and not through the carbon framework of the acenaphthene ring system. © 2023 The Authors. Published by American Chemical Society.
Original languageBritish English
Pages (from-to)16084-16100
Number of pages17
JournalInorg. Chem.
Volume62
Issue number39
DOIs
StatePublished - 2023

Keywords

  • Crystal atomic structure
  • Ligands
  • Mercury compounds
  • Metal complexes
  • Nuclear magnetic resonance spectroscopy
  • Palladium compounds
  • Phosphorus compounds
  • Platinum compounds
  • Selenium compounds
  • Silver compounds
  • Single crystals
  • Transition metals
  • Acenaphthene
  • Bidentate ligands
  • Block metals
  • Borane complexes
  • Lone pair
  • Mercury complex
  • Multinuclear NMR
  • NMR data
  • Transition-metal complex
  • X- ray diffractions
  • Chlorine compounds

Fingerprint

Dive into the research topics of 'Phosphine and Selenoether peri-Substituted Acenaphthenes and Their Transition-Metal Complexes: Structural and NMR Investigations: Inorganic Chemistry'. Together they form a unique fingerprint.

Cite this