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Enhancing Reactivity of Directly íObservable B–H–Pt Interactions through Conformational Rigidity

TitleEnhancing Reactivity of Directly íObservable B–H–Pt Interactions through Conformational Rigidity
Publication TypeJournal Article
Year of Publication2016
AuthorsPal, S, Drover, MW, Patrick, BO, Love, JA
JournalEuropean Journal of Inorganic Chemistry
Volume2016
Pagination2403–2408
ISSN1099-0682
KeywordsAgostic interactions, B–H functionalization, platinum, Scorpionate ligands
Abstract

We report for the first time the direct syntheses of trimethylplatinum(IV) complexes supported by bis(pyrazolyl)dihydridoborate (Bp) and bis(3,5-dimethylpyrazolyl)dihydridoborate (Bp*) ligands from the corresponding dimethylplatinum(II) complexes. X-ray crystallographic and multinuclear NMR characterization of the trimethylplatinum(IV) complexes reveal agostic B–H–Pt interactions. Solid-state analysis reveals that BpPtIVMe3 adopts a dinuclear structure featuring an intermolecular B–H–Pt bridge, whereas Bp*PtIVMe3 adopts a mononuclear structure containing an intramolecular B–H–Pt bridge. Addition of acetonitrile leads to cleavage of the weakly coordinating B–H–Pt interactions, and in the case of Bp*PtIVMe3, leads to hydroboration of acetonitrile. The B–H fragment interacting with the PtIV center in Bp*PtIVMe3 was also found to react with methanol to form a methoxy-bridged complex. DFT calculations were employed to investigate the structural contributions to the difference in the reactivity of the Bp- and Bp*-supported complexes.

URLhttp://dx.doi.org/10.1002/ejic.201501305
DOI10.1002/ejic.201501305