3 years ago

Borane-Stabilized Isomeric Dimers of the Phosphaethynolate Anion

Borane-Stabilized Isomeric Dimers of the Phosphaethynolate Anion
Andrew R. Jupp, Hansjörg Grützmacher, Douglas W. Stephan, Riccardo Suter, Kevin M. Szkop
The reactions of the phosphaethynolate anion ([PCO]−) with a range of boranes were explored. BPh3 and [PCO]− form a dimeric anion featuring P−B bonds and is prone to dissociation at room temperature. The more Lewis acidic borane B(C6F5)3 yields a less symmetric dimer of [PCO]− with P−B and P−O bonds. Less sterically demanding HB(C6F5)2 and H2B(C6F5) boranes form a third isomer with [PCO]− featuring both boranes bound to the same phosphorus atom. Despite the unexpected thermodynamic preference for P-coordination, computational data illustrate that electronic and steric features impact the binding modes of the resulting dianionic dimers. When two become one: The phosphaethynolate anion ([PCO]−) can interact with different boranes through the O or P terminus to give transient monomeric species. The Lewis acids mediate and stabilize the subsequent dimerization to give constitutional isomers of stable dimers (see scheme).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201708646

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