Abstract
The reactions of acrylonitrile (AN) with palladium alkyl complexes that contain bisphosphine ligands, P∧P = Ph2P(CH2)3PPh2 (a, dppp), Me2P(CH2)2PMe2 (b, dmpe), [Ph2B(CH2PPh2)2]- (c, Ph2BP2), were studied. (P∧P)PdMeCl (1a,b) reacts with [Li(Et2O)2.8][B(C6F5)4] and AN to form N-bound AN adducts (P∧P)PdMe(NCCHCH2)+ (3a,b). 3b inserts AN to form [(dmpe)Pd(CHEtCN)]nn+ (4b). Sequential reaction of [ASN][(Ph2BP2)PdMe2] (1c, ASN = 5-azoniaspiro[4.4]nonane) with [HNMe2Ph][B(C6F5)4] and AN affords the N-bound adduct (Ph2BP2)PdMe(NCCHCH2) (3c), which reacts to form [(Ph2BP2)Pd(CHEtCN)]n (4c). IR data suggest that the Pd units of 4b,c are aggregated by PdCHEtCN- - -Pd bridges. 4b reacts with PPh3 to form (dmpe)Pd(CHEtCN)(PPh3)+ (5b). 4c reacts with PMe3 and with pyridine (py) to form (Ph2BP2)Pd(CHEtCN)(L) (L = PMe3 (6c), py (7c)). The characterization of 5b, 6c, and 7c confirms the 2,1 AN insertion of 3b,c. The rate constants for AN insertion (kobs,AN, 23 °C) vary in the order 3c (1.12(3) × 10-3 s-1) > 3b (3.33(5) × ...
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