The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide.

Alkylation of spiro[fluorene-9,3'-indazole] at N(1) and N(2) with tBuCl affords the nitrenium cations [C6 H4 N2 (tBu)C(C12 H8 )][BF4 ], 1 and 2, respectively. Compound 1 converts to 2 over the temperature range 303-323 K with a free energy barrier of 28±5 kcal mol-1 . Reaction of 1 with PMe3 afforded the N-bound phosphine adduct [C6 H4 N(tBu)N(PMe3 )C(C12 H8 )]BF4 ] 3. However, phosphines attack 2 at the para-carbon atom of the aryl group with concurrent cleavage of N(2)-C(1) bond and proton migration to C(1) affording [(R3 P)C6 H3 NN(tBu)CH(C12 H8 )][BF4 ] (R=Me 4, nBu 5). Analogous reactions of 1 and 2 with the carbene SIMes prompt attack at the para-carbon with concurrent loss of H. affording the radical cation salts [(SIMes)C6 H3 N(tBu)NC(C12 H8 ). ][BF4 ] 6 and [(SIMes)C6 H3 NN(tBu)C(C12 H8 ). ][BF4 ] 7, whereas reaction of 2 with BAC gives the Lewis acid-base adduct, [C6 H4 N(BAC)N(tBu)C(C12 H8 )][BF4 ] 8. Finally, reactions of 1 and 2 with KPPh2 result in electron transfer affording (PPh2 )2 and the persistent radicals C6 H4 N(tBu)NC(C12 H8 ). and C6 H4 NN(tBu)C(C12 H8 ). . The detailed reaction mechanisms are also explored by extensive DFT calculations.