Facile addition of E-H bonds to a dicarbondiphosphide

Charge transfer at P atoms in an N-heterocyclic carbene stabilized 6π-electron aromatic dicarbondiphosphide 1 has been observed upon interaction with a variety of small molecule substrates that feature a polar E-H bond (E = C, N, and O). As a result, these P atoms exhibit fleeting nucleophilicity and electrophilicity behaving as potential independent active sites, which effect the spontaneous addition of E-H bonds leading to a series of unsymmetrical 1,3-diphosphetane frameworks bearing P-C ( 2 ), P-N ( 6 and 7 ), and P-O bonds ( 8b , 8c , and 9 ). In addition, 1,3-diphosphetanium salts have been achieved when X-type substituents are weakly coordinating ( i.e. [(CN) 2 CH] − ( 3 ), I − ( 4 ), and [(PhOH) 2 PhO] − ( 10 )). The mechanisms of such transformations are investigated using density functional theory calculations. Charge transfer at P atoms in an N-heterocyclic carbene stabilized 6π-electron aromatic dicarbondiphosphide 1 has been observed upon interaction with a variety of small molecule substrates that feature a polar E-H bond (E = C, N, and O).