Reaction of di-μ-dichloro-bis(N,N-dimethylbenzylamine-C2,N)dipalladium(II) with diphosphines. Six-membered ring complexes bearing spiro rings
摘要:
Reactions of [Pd(C6H4CH2NMe2-C-2,N)(mu-Cl)](2) with diphosphines (diphos) such as dppf (a), dpmf (b), dppm (c), dppe (d) and dppp (e) gave [PdCl(C6H4CH2NMe2-C-2,N)](2)(mu-diphos) (2). Complexes 2 (a, b, d and e) reacted with NaPF6 to produce chelate complexes [Pd(C6H4CH2NMe2-C-2,N)(diphos-P,P')][PF6] (3), whereas 2c gave a six-membered ring complex [Pd-2(C6H4CH2NMe2-C-2,N)(2)(mu-Cl)(mu-dppm)][PF6] (4c) bearing two exocyclic rings shared by each palladium atom. This complex was regenerated to 2e by treatment with [NEt3(CH2Ph)]Cl. Treatment of 3 (a, d and e) with one equiv. of aq. HCl caused protonation at the coordinate nitrogen atom to yield [Pd(C6H4CH2NHMe2-C-2)(Cl)(diphos-P,P')][PF6] (5) (a, d and e). Reaction of 4e with aq. HCl in a 1:1 molar ratio led to protonation at one C-N chelating ring to give [Pd-2(Cl)(C6H4CH2-NMe2- C-2,N)(C6H4CH2NHMe2-C-2)(mu-Cl)(mu-dppm)][PF6] (6c). The structures of 2a, 3e, 4c, 5a and 6c were confirmed by X-ray analyses. (C) 2000 Elsevier Science S.A. All rights reserved.
Dinuclear bridged biphosphinic and mononuclear cyclopalladated complexes of benzylamines: Synthesis, structural characterization and antitumor activity
Reaction of chloro-bridged dinuclear palladacycles, [Pd-2(C,N)-C6H4CH2NH(R)}(2)(mu-Cl)(2)](R = Et (1a); R = t-Bu (1b)) with pyridine and PPh3 in the 1:2 M ratio at room temperature was used to prepare the mononuclear complexes, [Pd(C,N)-C6H4CH2NH(R)Cl(L)] (R = Et and L = Py (2a); R = t-Bu and L = PPh3 (2b)). Bridged biphosphinic palladacycle, [Pd-2(C,N-dmba)(2)(mu-dppe)(Cl)(2)] (2c), (where dmba = N,N-dimethylbenzylamine and dppe = 1,2-bis(diphenylphosphino)ethane) has been also synthesized. The complexes were fully characterized by elemental analysis, IR and NMR spectroscopies. In addition, the solid structures of palladacycles 2a and 2c were studied by single-crystal X-ray crystallography. In vitro cytotoxicity assays of the cyclopalladated complexes, (2a-2c) and cisplatin were evaluated against the Hela (human cervix carcinoma), HT-29 (colon cancer cell line), K562 (leukemia cancer cell line) and MDA-MB-468 (human breast carcinoma). The complexes 2a-2c display IC50 values in a mu M range better than that of the antitumor drug cisplatin. (C) 2012 Elsevier Ltd. All rights reserved.