Incorporating trisubstituted boranes into multidentate ligand platforms has allowed unprecedented types of cooperative metal-ligand transformations and other forms of ligand-centered reactivity to be realized. In this contribution, we will describe the synthesis, coordination chemistry, and reactivity of a new class of diphosphines bridged by 1,8,10,9-triazaboradecalin (TBD). Despite the very low Lewis acidity of B in TBD, treating metal TBDPhos complexes with water, alcohols, and hydrated fluoride salts results in net trans addition of O-H or F-H across the bridgehead B-N bond in the TBD backbone. Control experiments conducted in the absence of a proton source reveal that N protonation is important for achieving the observed reactivity at B. Collectively, reactions involving B and N in ligated TBDPhos are reminiscent of cooperative metal-ligand reactions involving M-N bonds. As such, we define these TBDPhos reactions as cooperative ligand-centered reactivity. Potential applications in small molecule sensing and catalysis will be discussed.

Cooperative ligand-centered reactivity in triaminoborane-bridged diphosphine complexes

254th National Meeting (2017)

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