235084-35-2Relevant academic research and scientific papers
Multidonor ligands. 3. Cyclopalladation of py{SCH2C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp3)-H bond activation
Vicente, José,Chicote, María-Teresa,Rubio, Concepción,Ramírez De Arellano, M. Carmen,Jones, Peter G.
, p. 2750 - 2759 (2008/10/08)
[PdCl2(NCPh)2] reacts with R-carbonylmethylenethiopyridines [py{SCH2C(O)R}-2] to give, depending on the substituent R and the reaction conditions, [Pd{py{SCHC(O)Ph}-2}(μ-Cl)2Pd-{py{SCH2C(O)Ph}-2}Cl] or the coordination complexes [Pd{py{SCH2C(O)R}-2}2Cl2] (R = Ph, Me, OMe). The latter can be doubly deprotonated by a base (Na2CO3 or NaH) to give dicyclometalated complexes cis-[Pd{py{SCHC(O)R}-2}2]. These transmetalate one ligand to [PdCl2(NCPh)2] to give [Pd{py{SCHC(O)R}-2}(μ-Cl)]2, which in turn reacts with (Me4N)Cl or with monodentate ligands L or with MeCN in the presence of AgClO4 to give anionic Me4N[Pd{py{SCHC(O)Ph}-2}Cl2], neutral [Pd{py{SCHC(O)R}-2}Cl(L) [R = Ph, L = PPh3, py{SCH2C(O)Ph}-2, tBuNC, NH2CH(Me)Ph, pyridine (py), tetrahydrothiophene (tht); R = Me, L = PPh3, py, tht], or cationic [Pd{py{SCHC(O)R}-2}(NCMe)2]ClO4 (R = Ph, Me, OMe) complexes, respectively. The latter react with PPh3 or with bidentate ligands to give complexes [Pd{py{SCHC(O)Ph}-2}(NCMe)(PPh3)]ClO4 or [Pd{py{SCHC(O)Ph}-2}L2]ClO4 [L = PPh3, L2 = N,N,N′,N′-tetramethylethylenediamine (tmeda) or 2,2′-bipyridine (bipy)]. The crystal structures of[Pd{py{SCHC(O)R}-2}2] and [Pd{py{SCHC(O)R}-2}Cl{py{SCH2C(O)R}-2}] have been determined.
