Synthesis and activity studies in vitro and in vivo of a new series of malonato-platinum(II) complexes containing sulfide and phosphine ligands

Sampedro, F.; Molins-Pujol, A.M.; Ruiz, J.I.; Santaló, P.; Bonal, J.; Pueyo, M; Llagostera, Montserrat; Sánchez‐Ferrando, Francisco

doi:10.1016/0223-5234(92)90139-r

Cited by 5 publications

(4 citation statements)

References 13 publications

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“…This result is consistent with two unique species, each with their own unique phosphorus environment; such is the case when two donor ligands on the platinum metal node are the same (i.e., carboxylate‐Pt‐carboxylate or pyridyl‐Pt‐pyridyl). A plausible explanation for the monomeric nature of 6 is the favorable chelation that can occur with the methylene‐spaced carboxylate donor, similar to what is observed in malonato‐bis(phosphine) Pt II systems 14…”

Section: Resultsmentioning

confidence: 99%

“…The mixtures were heated to 40 8C and allowed to stir for 3 hours. [14] Dipyridyl linker 3 can coordinate two molecules of 1 and if the carboxylate linker can bridge those two platinum nodes, a dimer will preferentially form instead of a more complex structure. The SCCs were then characterized by 1 H and 31 P{ 1 H} NMR spectroscopies and electrospray ionization mass spectrometry (ESI-MS).…”

Section: Flexible Sccsmentioning

confidence: 99%

“…A plausible explanation for the monomeric nature of 6 is the favorable chelation that can occur with the methylene-spaced carboxylate donor, similar to what is observed in malonato-bis(phosphine) Pt II systems. [14] Dipyridyl linker 3 can coordinate two molecules of 1 and if the carboxylate linker can bridge those two platinum nodes, a dimer will preferentially form instead of a more complex structure. To probe this effect, sodium n-heptadecanoate dibasic 2 d (Scheme 3) was specifically chosen since the covalent bond distance, as determined by a Merck molecular force field (MMFF) [15] calculation, between the anionic coordinating oxygen atoms is 19.85 , while the covalent bond distance between the coordinating nitrogen atoms of the dipyridyl linker 3 is 16.90 .…”

Section: Flexible Sccsmentioning

confidence: 99%

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Multi‐Component Coordination‐Driven Self‐Assembly: Construction of Alkyl‐Based Structures and Molecular Modelling

Pollock

Cook

Schneider

et al. 2013

Chemistry An Asian Journal

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The design of supramolecular coordination complexes (SCCs) is typically predicated on the use of rigid molecular building blocks through which the structural outcome is determined based on the number and orientation of labile coordination sites on metal acceptors, and the angularity of the ligand donors that are to bridge these nodes. Three-component systems extend the complexity of self-assembly by utilizing two different Lewis base donors in concert with a metal that favors a heteroligated coordination environment. The thermodynamic preference for heteroligation provides a new design principle to the formation of SCCs, wherein multicomponent architectures need not employ only rigid donors. Herein, we exploit the self-selection processes of bis(phosphine) Pt(II) metal centers which favor mixed Pt(pyridyl)(carboxylate) coordination spheres over their homoligated counterparts, specifically using alkyl-based dicarboxylate ligands instead of traditionally rigid phenyl, alkenyl, or ethynyl variants. Using this mode of assembly, flexible-based 2D and 3D SCCs containing long alkyl chains were synthesized and characterized. Density functional theory (DFT) and natural population analysis (NPA) calculations were performed on model systems to probe the thermodynamic preference for heteroligated coordination spheres in the experimental systems.

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Section: Resultsmentioning

confidence: 99%

Section: Flexible Sccsmentioning

confidence: 99%

Section: Flexible Sccsmentioning

confidence: 99%

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Multi‐Component Coordination‐Driven Self‐Assembly: Construction of Alkyl‐Based Structures and Molecular Modelling

Pollock

Cook

Schneider

et al. 2013

Chemistry An Asian Journal

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“…Ligand structural compositions beyond am(m)ines, specifically Pt-phosphine or mixed phosphine/am(m)ine complexes, also show considerable antitumor activity. − Complexes with open or exchangeable coordination positions appear to operate in the more classic cisplain-like manner via DNA adduct formation, ,,,,,− while coordinatively saturated structures, especially those with chelating lipophilic phosphines, are proposed to function by a unique anti-mitochondrial mechanism. ,, This functional divergence may be the reason that these cationic complexes are active against cisplatin-resistant cells.…”

Section: Introductionmentioning

confidence: 99%

Utilizing Redox-Mediated Bergman Cyclization toward the Development of Dual-Action Metalloenediyne Therapeutics

et al. 2013

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Reaction of 2 equiv of 1,2-bis((diphenylphosphino)ethynyl)benzene (dppeb, 1) with Pt(cod)Cl2 followed by treatment with N2H4 yields the reduced Pt(0) metalloenediyne, Pt(dppeb)2, 2. This complex is stable to both air oxidation and metal-mediated Bergman cyclization under ambient conditions due to the nearly idealized tetrahedral geometry. Reaction of 2 with 1 equiv of I2 in the presence of excess 1,4-cyclohexadiene (1,4-CHD) radical trap rapidly and near-quantitatively generates the cis-Bergman-cyclized, diiodo product 3 ((31)P: δ = 41 ppm, J(Pt-P) = 3346 Hz) with concomitant loss of 1 equiv of uncyclized phosphine chelate ((31)P: δ = -33 ppm). In contrast, addition of 2 equiv of I2 in the absence of additional radical trap instantaneously forms a metastable Pt(dppeb)2(2+) intermediate species, 4, that is characterized by δ = 51 ppm in the (31)P NMR (J(Pt-P) = 3171 Hz) and ν(C≡C) = 2169 cm(-1) in the Raman profile, indicating that it is an uncyclized, bis-ligated complex. Over 24 h, 4 undergoes ligand exchange to form a neutral, square planar complex that spontaneously Bergman cyclizes at ambient temperature to give the crystalline product Pt(dppnap-I2)I2 (dppnap-I2 = (1,4-diiodonaphthalene-2,3-diyl)bis(diphenylphosphine)), 5, in 52% isolated yield. Computational analysis of the oxidation reaction proposes two plausible flattened tetrahedral structures for intermediate 4: one where the phosphine core has migrated to a trans-spanning chelate geometry, and a second, higher energy structure (3.3 kcal/mol) with two cis-chelating phosphine ligands (41° dihedral angle) via a restricted alkyne-terminal starting point. While the energies are disparate, the common theme in both structures is the elongated Pt-P bond lengths (>2.4 Å), indicating that nucleophilic ligand substitution by I(-) is on the reaction trajectory to the cyclized product 5. The efficiency of the redox-mediated Bergman cyclization reaction of this stable Pt(0) metalloenediyne prodrug and resulting cisplatin-like byproduct represents an intriguing new strategy for potential dual-threat metalloenediyne therapeutics.

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Carboplatin 41575‐94‐4

2004

Sax's Dangerous Properties of Industrial Materials

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Synthesis and activity studies in vitro and in vivo of a new series of malonato-platinum(II) complexes containing sulfide and phosphine ligands

Cited by 5 publications

References 13 publications

Multi‐Component Coordination‐Driven Self‐Assembly: Construction of Alkyl‐Based Structures and Molecular Modelling

Multi‐Component Coordination‐Driven Self‐Assembly: Construction of Alkyl‐Based Structures and Molecular Modelling

Utilizing Redox-Mediated Bergman Cyclization toward the Development of Dual-Action Metalloenediyne Therapeutics

Carboplatin 41575‐94‐4

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