647824-13-3Relevant academic research and scientific papers
Synthesis and reactivity of cyclometallated platinum (II) compounds containing [C,N,N′] terdentate ligands: Crystal structures of [PtCl{(CH3)2N(CH2)3NCH(4-ClC 6H3)}], [PtCl{(CH3)2N(CH 2)3NCH(2-ClC6H3)}]
Capapé, Alejandro,Crespo, Margarita,Granell, Jaume,Font-Bardía, Mercè,Solans, Xavier
, p. 4309 - 4318 (2007/10/03)
The reaction of compound cis-[PtCl2(dmso)2] with ligands RCHN(CH2)3NMe2 (1a-1h) in which R is a phenyl group containing substituents such as Cl, F, Me, NO2 and MeO produced compounds [PtCl2{(CH3)2N(CH 2)3NCHR}] (2), as mixtures of Z and E isomers. When treated with an equimolar amount of sodium acetate in refluxing methanol compounds 2 gave cyclometallated platinum compounds 3 containing a terdentate [C,N,N′] ligand. The obtained compounds were fully characterized including structure determinations for compounds 3a, 3b and 3e. The effects of the substituents in the regioselectivity of the cyclometallation reaction and the reactivity of 3a and 3b with mono and bidentate phosphines were also studied.
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 (2007/10/03)
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).
