Phosphine and selenoether peri-substituted acenaphthenes and their transition metal complexes : structural and NMR investigations
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 L1HgCl 2 complex, the main coupling pathway is via the metal atom and not through the carbon framework of the acenaphthene ring system.
Citation
Zhang , L , Christie , F , Tarcza , A , Lancaster , H , Taylor , L , Buehl , M , Malkina , O , Woollins , J D , Carpenter-Warren , C L , Cordes , D B , Slawin , A M Z , Chalmers , B A & Kilian , P 2023 , ' Phosphine and selenoether peri-substituted acenaphthenes and their transition metal complexes : structural and NMR investigations ' , Inorganic Chemistry , vol. Articles ASAP . https://doi.org/10.1021/acs.inorgchem.3c02255
Publication
Inorganic Chemistry
Status
Peer reviewed
ISSN
0020-1669Type
Journal article
Description
Funding: This work was financially supported by the School of Chemistry, University of St Andrews, and COST actions CM0802 PhoSciNet and SM1302 SIPs. B.A.C. and P.K. thank Dr D. Dawson for the acquisition of solid-state NMR spectra. L.Z. thanks the CSC-St Andrews Scholarship for the PhD funding. O.M. acknowledges the support from Slovak grant agencies APVV (APVV-19-0516) and VEGA (Grant No. 2/ 0135/21). In order to meet institutional and research funder open access requirements, any accepted manuscript arising shall be open access under a Creative Commons Attribution (CC BY) reuse licence with zero embargo.Collections
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