172987-87-0Relevant academic research and scientific papers
Isocyanide Insertion into the Palladium-Carbon Bond of Complexes and the Reactivity of the Products toward Norbornadiene; X-Ray Crystal Structure of (bpy)Cl>
Delis, Johannes G. P.,Aubel, Peter G.,Leeuwen, Piet W. N. M. van,Vrieze, Kees,Veldman, Nora,Spek, Anthony L.
, p. 2233 - 2234 (1995)
The first examples of isocyanide insertion into methyl-palladium-chloride complexes containing 2,2'-bipyridine (bpy) and phenanthroline (phen), the X-ray crystal structure of (bpy)Cl> and the novel insertion of norbornadiene into the Pd-C(=NR)Me bond are presented; the insertion mechanism of isocyanides involves displacement of the chloride and a subsequent, slower migration of the methyl group to the precoordinated isocyanide.
Insertion of unsaturated hydrocarbons into the palladium-carbon bond of complexes (N?N)Pd(C(=N-2,6-Me2Ph)Me)X (N?N = bpy, phen; X = Cl, Br, I, BF4): A structural and mechanistic study
Delis, Johannes G. P.,Aubel, Peter G.,Vrieze, Kees,Van Leeuwen, Piet W. N. M.,Veldman, Nora,Spek, Anthony L.
, p. 4150 - 4160 (2008/10/08)
The reactivity of Pd-carboimine complexes toward unsaturated hydrocarbon bonds has been studied. Insertion of norbornadiene and norbornene into the Pd-C bond of the neutral complexes (N?N)Pd(C(=N-2,6-Me2C6H3)Me)X (X = Cl (1), Br (2), I (3); N?N = 2,2′-bipyridine (bpy, a), 1,10-phenanthroline (phen, b)) afforded quantitatively the novel and stable complexes [(N?N)Pd(C7H8C(=NR)Me)]X and [(N?N)Pd(C7H10C(=NR)Me)]X (R = 2,6-Me2C6H3). Insertion reactions of the unstrained unsaturated hydrocarbons ethylene, propylene, 3-methyl-1,2-butadiene, and acetylene with the cationic complexes [(N?N)Pd-(C(=NR)Me)]X (N?N = bpy, phen; R = 2,6-Me2C6H3; X = BF4) provided the complexes [(N?N)-Pd(C2H4C(=NR)Me)]X, [(N?N)Pd(C3H6C(=NR)Me)]X, [(N?N)Pd(C5H8C(=NR)Me)]X, and [(bpy)Pd(C2H2C(=NR)Me)]X. The remarkable stability of these products is caused by the strong coordination of the carboimine nitrogen to the palladium center. Reaction of 1a and 1b with HC≡CCOOMe gave, instead of an insertion product, the Michael addition product (N?N)Pd[C(=CH2)N(2,6-Me2C6H 3)(CH=CHCOOMe)]Cl. Kinetic measurements carried out on the norbornadiene insertion reactions with 1a,b, 2a, and 3a revealed that the reactions are first order in the palladium concentration and occur via a norbornadiene concentration-independent and dependent pathway.
