Phosphorus-Bismuth Peri-Substituted Acenaphthenes: A Synthetic, Structural, and Computational Study

Phillip S Nejman; Thomasine E Curzon; Michael Bühl; David McKay; J Derek Woollins; Sharon E Ashbrook; David B Cordes; Alexandra M Z Slawin; Petr Kilian

doi:10.1021/acs.inorgchem.0c00317

Phosphorus-Bismuth Peri-Substituted Acenaphthenes: A Synthetic, Structural, and Computational Study

Inorg Chem. 2020 Apr 20;59(8):5616-5625. doi: 10.1021/acs.inorgchem.0c00317. Epub 2020 Apr 9.

Authors

Phillip S Nejman¹, Thomasine E Curzon¹, Michael Bühl¹, David McKay¹, J Derek Woollins², Sharon E Ashbrook¹, David B Cordes¹, Alexandra M Z Slawin¹, Petr Kilian¹

Affiliations

¹ EaStChem School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 ST, U.K.
² Department of Chemistry, Khalifa University, P.O. Box 127788, Abu Dhabi, United Arab Emirates.

PMID: 32271559
DOI: 10.1021/acs.inorgchem.0c00317

Abstract

A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri positions were synthesized and fully characterized, including single-crystal X-ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P-Bi bond. The series includes the phosphine-bismuthine Acenap(PiPr₂)(BiPh₂) (2; Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(PiPr₂)(BiPhX) (5-8 and 10; X = BF₄^-_, Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl)-substituted [Acenap(PiPr₂)]₂BiPh (3) shows a large through-space coupling of 17.8 Hz, formally ^8TSJ_PP. Coupling deformation density calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two ³¹P nuclei. Several synthetic routes toward the phosphine-diiodobismuthine Acenap(PiPr₂)(BiI₂) (9) have been investigated; however, the purity of this, surprisingly thermally stable potential synthon, remains poor.