Tris(diphenylphosphinomethyl)phenylborate and tris(diisopropylphosphinomethyl)phenylborate are well established as strong field facially capping ligands; these ligands have been classified as strongly donating scorpionates. Despite the broad utility of this class of ligands, a systematic investigation into the role of the borate negative charge at phosphorous-bound metal fragments has not been carried out. The Fischer laboratory has pursued this objective by two strategies: (a) the installation of electron withdrawing metal tricarbonyl fragments on the bridgehead boron phenyl substituent and (b) the synthesis of new tris(diphenylphosphinomethyl)phenylborates with electron donating and electron withdrawing substituents at the 3,5-positions of this borate phenyl group. The new members of the tris(diphenylphosphinomethyl)phenylborate family have been fully characterized in both solution and the solid-state. The subtle impact of these ligand modifications towards zerovalent metal tricarbonyl fragments at phosphorous has been explored by X-ray crystallography, IR and NMR spectroscopy and cyclic voltammetry.

Prospects for tuning Tris(diphenylphosphinomethyl)phenylborate donation via introduction of organic and organometallic substituents at the bridgehead boron phenyl group

255th National Meeting (2018)

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