Interaction of cystamine with palladium(II) monoethanolaminate complex: Crystal structure of [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O

Gasanov, Kh. I.; Анцышкина, А. С.; Садиков, Г. Г.; Иванова, Н. А.; Mirzai, D. I.; Ефименко, И. А.; Сергиенко, В. С.

doi:10.1134/1.1496058

Cited by 11 publications

(3 citation statements)

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“…При этом продукт расщепления цистамина -меркамин в зависимости от условий проведения синтеза с палладием (II) и платиной (II) образует моно-, би-, три-и шестиядерные комплексы с различной координацией и конфигурацией [34][35][36][37].…”

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Study of Interaction Platinum Salts (Ii) and Palladium (Ii) on the Biologically Active Ligand

Azizova¹,

Tagiyev²,

Gyulalov³

et al. 2014

European Researcher

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Study of Interaction Platinum Salts (Ii) and Palladium (Ii) on the Biologically Active Ligand

Azizova¹,

Tagiyev²,

Gyulalov³

et al. 2014

European Researcher

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“…Solid-state molecular structure of 5 a. Hydrogen atoms and solvent molecules are omitted for clarity. Selected bond lengths [] and angles [8]: Pd1-C1 1.937(2), Pd1-N3 1.980(2), Pd1-O2 2.1102(18), Pd1-Cl1 2.3031(7), C1-Pd1-N3 88.60(9), C1-Pd1-O2 170.05(9), N3-Pd1-O2 81.67(8), C1-Pd1-Cl1 97.89(7), N3-Pd1-Cl1 172.90(6), O2-Pd1-Cl1 91.94(5).…”

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confidence: 99%

Chiral Palladium(II) Complexes Possessing a Tridentate N‐Heterocyclic Carbene Amidate Alkoxide Ligand: Access to Oxygen‐Bridging Dimer Structures

et al. 2008

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N-Heterocyclic carbenes (NHCs) and their palladium complexes have been developed to facilitate the formation of carbon-carbon and carbon-heteroatom bonds.[1] NHC complexes exhibit unique chemical properties such as strong Pd-NHC s bonding, which enhances the stabilities of active organometallic compounds relative to conventional phosphane complexes.[2] Moreover, chiral NHC ligands have been synthesized to promote asymmetric catalysis. [3] Most of the chiral NHC ligands that have been utilized for asymmetric Pd II catalysis are monodentate, as Lee and Hartwig demonstrated moderate enantioselectivities (71-76 % ee) in a-arylation.[4] However, monodentate ligands caused practical difficulties including concomitant formation of inactive palladium-ligand complexes, such as those with a trans conformation. Bidentate NHC ligands exhibited better stabilities and selectivities: Douthwaite reported better enantioselectivities (up to 92 % ee) for asymmetric allylic alkylation [5a, b] than reactions employing the corresponding monodentate ligand.[5c]We envisioned tridentate NHCs would enhance the stabilities of Pd II complexes and enantioselectivities of various asymmetric reactions. As depicted in Figure 1, we sought a "chiral {Pd(OAc) 2 } complex" and designed and synthesized novel chiral tridentate NHC-Pd II complexes (II). Notably, ligand systems with NHCs, amidates, and oxygen functionalities (a C,N,O triad) could exert high electron densities and strong coordination on the Pd II complexes to increase stabilities even in nucleophilic solvents such as water and alcohols. Therefore, labile ligands such as water, alcohols, and acetonitrile are likely to be removed easily and thus enhance the reactivities and efficiencies of NHC-Pd catalysts.We report herein the synthesis of chiral tridentate NHC-Pd II complexes and their applications in an asymmetric oxidative Heck-type reaction as a proof of concept.The preparation of chiral ligands 4 is shown in Scheme 1. Hydroxyamide compounds 2 were prepared by reduction of amino acids 1 and subsequent N-alkylation with bromoacetyl bromide. Treatment of 2 with benzimidazole in the presence of KOH in DMF provided compounds 3, which were subjected to methylation to yield the amido alcohol substituted benzimidazolium salts 4. The structure was confirmed by 1 H NMR spectroscopic analysis; new peaks assigned to the NCH 3 appeared at d = 4.18 (4 a) and 4.15 ppm (4 b). Also, the imidazole H resonances shifted significantly as expected for iodine salts, appearing at d = 9.55 (4 a) and 9.50 ppm (4 b).Because direct coordination of ligands 4 to palladium was not efficient under numerous conditions, the ligands were transferred to palladium via silver NHC complexes.[6] As described in Scheme 2, compounds 4 a and 4 b were treated with Ag 2 O in CH 2 Cl 2 to give silver NHC complexes.

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“…Notably, the Pd À N bond lengths of both structures are shortened (1.980(2) for 5 a and 1.978(3) for 6 a) relative to other PdÀN bonds, such as with protonic amines, azides, and imines. [7] This peculiar structural feature indicates that the PdÀN bonding is anionic coordination. For example, the geometry about N2 in 6 a is approximately trigonal planar as shown by the torsion angle (10.88) for C3•••C12•••Pd1•••N2 and the sum of the bond angles (355.808).…”

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confidence: 99%

Chiral Palladium(II) Complexes Possessing a Tridentate N‐Heterocyclic Carbene Amidate Alkoxide Ligand: Access to Oxygen‐Bridging Dimer Structures

et al. 2008

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Katalysatoren mit Biss: Chirale PdII‐Komplexe wurden mit dreizähnigen Liganden aus N‐heterocyclischem Carben, Amidat und Alkoxid hergestellt. Dimere und monomere Formen dieser Komplexe lassen sich durch Einwirkung von Säuren und Basen ineinander umwandeln (siehe Schema). Die Katalysatoren sind in asymmetrischen Heck‐Reaktionen aktiv und ergeben deutlich bessere Enantioselektivitäten als bisherige Methoden.

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Interaction of cystamine with palladium(II) monoethanolaminate complex: Crystal structure of [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O

Cited by 11 publications

References 1 publication

Study of Interaction Platinum Salts (Ii) and Palladium (Ii) on the Biologically Active Ligand

Study of Interaction Platinum Salts (Ii) and Palladium (Ii) on the Biologically Active Ligand

Chiral Palladium(II) Complexes Possessing a Tridentate N‐Heterocyclic Carbene Amidate Alkoxide Ligand: Access to Oxygen‐Bridging Dimer Structures

Chiral Palladium(II) Complexes Possessing a Tridentate N‐Heterocyclic Carbene Amidate Alkoxide Ligand: Access to Oxygen‐Bridging Dimer Structures

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