Phosphine and selenoether peri-substituted acenaphthenes and their transition metal complexes: structural and NMR investigations

Lutao Zhang, Francesca Christie, Anna Tarcza, Helena Lancaster, Laurence Taylor, Michael Buehl, Olga Malkina, J Derek Woollins, Cameron Lewis Carpenter-Warren, David Bradford Cordes, Alexandra Martha Zoya Slawin, Brian Alexander Chalmers*, Petr Kilian*

*Corresponding author for this work

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A series of peri-substituted acenaphthene-based phosphine selenoether bidentate ligands Acenap(iPr2P)(SeAr) (L1L4, 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 L1L4 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.
Original languageEnglish
JournalInorganic Chemistry
VolumeArticles ASAP
Early online date18 Sept 2023
Publication statusE-pub ahead of print - 18 Sept 2023


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