@article {EJIC:EJIC201501305, title = {Enhancing Reactivity of Directly {\'\i}Observable B{\textendash}H{\textendash}Pt Interactions through Conformational Rigidity}, journal = {European Journal of Inorganic Chemistry}, volume = {2016}, number = {15-16}, year = {2016}, pages = {2403{\textendash}2408}, 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{\textendash}H{\textendash}Pt interactions. Solid-state analysis reveals that BpPtIVMe3 adopts a dinuclear structure featuring an intermolecular B{\textendash}H{\textendash}Pt bridge, whereas Bp*PtIVMe3 adopts a mononuclear structure containing an intramolecular B{\textendash}H{\textendash}Pt bridge. Addition of acetonitrile leads to cleavage of the weakly coordinating B{\textendash}H{\textendash}Pt interactions, and in the case of Bp*PtIVMe3, leads to hydroboration of acetonitrile. The B{\textendash}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.}, keywords = {Agostic interactions, B{\textendash}H functionalization, platinum, Scorpionate ligands}, issn = {1099-0682}, doi = {10.1002/ejic.201501305}, url = {http://dx.doi.org/10.1002/ejic.201501305}, author = {Pal, Shrinwantu and Drover, Marcus W. and Patrick, Brian O. and Love, Jennifer A.} }