339524-73-1Relevant articles and documents
Novel structures of cyclometallated complexes of palladium(II) derived from terdentate ligands. Crystal and molecular structure of [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(X)] (X = Cl, Br, I)
Fernández, Alberto,Uría, Patricia,Fernández, Jesús J.,López-Torres, Margarita,Suárez, Antonio,Vázquez-García, Digna,Pereira, Ma. Teresa,Vila, José M.
, p. 8 - 19 (2001)
Treatment of N-(2-chlorobenzylidene)-N,N-dimethyl-1,3-propanediamine (1) and N-(2-bromo-3,4-(MeO)2-benzylidene)-N,N-dimethyl-1,3-propanediamine (20) with tris(dibenzylideneacetone)dipalladium(0) in toluene gave the mononuclear cyclometallated complexes [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(Cl)] (2) and [Pd{3,4-(MeO)2C6H2C(H)=NCH2CH 2CH2NMe2}(Br)] (21), respectively, via oxidative addition reaction with the ligand as a C,N,N terdentate ligand. Reaction of 2 with sodium bromide or iodide in an acetone-water mixture gave the cyclometallated analogues of 2, [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(Br)] (3) and [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(I)] (4), by halogen exchange. The X-ray crystal structures of 2, 3 and 4 were determined and discussed. Treatment of 2, 3, 4 and 21 with tertiary monophosphines in acetone gave the mononuclear cyclometallated complexes [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(L)(X)] (6: L = PPh3, X = Cl; 7: L = PPh3, X = Br; 8: L = PPh3, X = I; 9: L = PMePh2, X = Cl; 10: L = PMe2Ph, X = Cl) and [Pd{3,4-(MeO)2C6H2C(H)=NCH2CH 2CH2NMe2}(L)(Br)] (22: L = PPh3; 23: L = PMePh2; 24: L = PMe2Ph). A fluxional behaviour due to an uncoordinated CH2CH2CH2NMe2 could be determined by variable temperature NMR spectroscopy. Treatment of 2, 3 and 4 with silver trifluoromethanesulfonate followed by reaction with triphenylphosphine gave the mononuclear complex [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(PPh3)][F3CSO3] (11) where the Pd-NMe2 bond was retained. Reaction of 2, 3 and 4 with ditertiary diphosphines in a cyclometallated complex-diphosphine 2:1 molar ratio gave the binuclear complexes [{Pd[C6H4C(H)=NCH2CH2CH 2NMe2](X)}2(μ-L-L)][L-L = PPh2(CH2)4PPh2(dppb) (13, X = Cl; 14, X = Br; 15, X = I; L-L = PPh2(CH2)5PPh2(dpppe): 16, X = Cl; 17, X = Br; 18, X = I) with palladium-NMe2 bond cleavage. Treatment of 2, 3 and 4 with ditertiary diphosphines, in a cyclometallated complex-diphosphine 2:1, molar ratio and AgSO3CF3 gave the binuclear cyclometallated complexes [{Pd[C6H4C(H)=NCH2CH2CH 2NMe2]}2(μ-L-L)][F3CSO 3]2 (11: L-L = PPh2(CH2)4PPh2(dppb), X = Cl; 12: L-L = PPh2(CH2)5PPh2 (dpppe), X = Cl). Reaction of 2 with the ditertiary diphosphine cis-dppe in a cyclometallated complex-diphosphine 1:1 molar ratio followed by treatment with sodium perchlorate gave the mononuclear cyclometallated complex [Pd{C6H4C(H)=NCH2CH2CH 2NMe2}(cis-PPh2CH=CHPPh 2-P,P)][ClO4] (19).
