Jm. Boncella et La. Villanueva, REACTIONS OF UNSATURATED ELECTROPHILES WITH TRANS-(PME(3))(2)PD(PH)(NHPH), Journal of organometallic chemistry, 465(1-2), 1994, pp. 297-304
The complex trans-(PMe(3))(2)Pd(Ph)(NHPh)(1) reacts with the unsaturat
ed electrophiles CO2, RNCO (R = Ph, (1)Bu, 2,6-(PrC6H3)-Pr-i), Ph(2)C=
C=O and maleic anhydride. The less bulky substrates, CO2 and maleic an
hydride, react by net insertion into the Pd-N bond, while the bulky el
ectrophiles (1)BuNCO, (2,6-Pr-i-C6H3) NCO, and Ph(2)C=C=O react by N-H
addition. N-15 labeling experiments show that the initial product of
the reaction of phenylisocyanate with 1 is the Pd-N insertion product
which then tautomerizes to the N-H addition product.