Synthesis and Coordination Chemistry of Doubly-Tridentate Tripodal Pyridazine and Pyrimidine-Derived Ligands: Structural Interplay Between M2L and M2L2 (M = Ni and Pd) Complexes and Magnetic Properties of Iron(II) Complexes

2009 ◽  
Vol 62 (9) ◽  
pp. 1142 ◽  
Author(s):  
Christopher J. Sumby ◽  
Ben A. Leita ◽  
Boujemaa Moubaraki ◽  
Keith S. Murray ◽  
Peter J. Steel
Keyword(s):  
Magnetic Properties ◽  
Coordination Chemistry ◽  
Spin Crossover ◽  
Coordination Complexes ◽  
Planar Geometry ◽  
Tridentate Ligands ◽  
One Pot ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pd Complexes

The coordination chemistry of three bridging doubly-tridentate ligands, including the known compound 3,6-bis(di-2-pyridylmethyl)pyridazine (1), which is structurally similar to 1,4-bis(di-2-pyridylmethyl)phthalazine (2), and two pyrimidine-linked compounds 4,6-bis(di-2-pyridylmethyl)pyrimidine (3), and 4,6-bis(di-2-pyridylamino)pyrimidine (4), was investigated with FeII, NiII, and PdII metal salts. Ligands 3 and 4 were synthesized in one-pot reactions from easily obtained starting materials; compound 3 was synthesized from di-2-pyridylmethane and 4,6-diiodopyrimidine in 48% yield, while ligand 4 was prepared by reacting di-2-pyridylamine with 4,6-dichloropyrimidine in 27% yield. During the synthesis of 4, an additional compound, 4-chloro-6-(di-2-pyridylamino)pyrimidine (5), with only one tridentate binding site was obtained in 30% yield. Reactions of 1, 3, and 4 with FeII or NiII salts gave two types of complexes, either discrete M2L or M2L2 assemblies. The PdII complexes obtained were also characterized as discrete M2L complexes. The compounds were characterized by a combination of NMR and IR spectroscopy, microanalysis and X-ray crystallography. Noticeable differences in the structures obtained for NiII coordination complexes with the carbon-linked (3) and nitrogen-linked (4) ligands were observed, whereby the nitrogen linker adopted a trigonal planar geometry and prevented tridentate facial coordination of the octahedral metal centres. The magnetic properties of dinuclear FeII complexes of 1 were examined to see if they showed spin-crossover effects, a feature recently observed by others in other dinuclear helicate complexes, but the complexes remained high-spin at all temperatures between 300 and 2 K.

scholarly journals Σύνθεση και χαρακτηρισμός μεταλλικών πλειάδων υψηλού σπιν και μονομοριακών μαγνητών

2015 ◽  
Author(s):  
Εμμανουήλ-Αλέξανδρος Περιβολάρης
Keyword(s):  
Magnetic Properties ◽  
Coordination Chemistry ◽  
Chemical Reactivity ◽  
Atmospheric Oxygen ◽  
Organic Ligands ◽  
X Ray ◽  
Nickel Iron ◽  
X Ray Crystallography ◽  
Depth Study ◽  
Iron And Manganese

The combination of a-benzoin-oxime (aboH2) in the coordination chemistry of NiII leadsto the formation of octanuclear clusters which contain an unusual peroxo anion derivedby the reduction of atmospheric oxygen while the reducing agent appears to be theorganic ligand (aboH2) which was found within the clusters in its oxidized form as theanion of a-benzil monooxime (abmoH). The in-depth study of the above reaction systemand the chemical reactivity of the octanuclear cages led to the synthesis of a family ofNiII clusters which counts over 20 family members built around a ι6-δ 3:δ 3-Ο2 2-. Thecombination of pseudochalides and other organic ligands in the above reaction systemdid not alter the cores of the octanuclear clusters but caused significant structuralchanges which in turn drastically changed the magnetic properties of the clusters. Theclusters were characterized by X-ray crystallography, spectroscopic and physicalmethods while their magnetic properties were also investigated.In the second part of this thesis, was completed the study of the magnetic properties ofa family of hexanuclear MnIII cages, while was also studied the coordination chemistryof other oxime ligands in combination with nickel, iron and manganese.

scholarly journals 4-vinylpyridine derivatives: Protonation, methylation and silver(I) coordination chemistry

2021 ◽  
pp. 174751982198965
Author(s):  
Guoqi Zhang
Keyword(s):  
Mass Spectrometry ◽  
Schiff Base ◽  
Coordination Chemistry ◽  
Elemental Analysis ◽  
Silver Complex ◽  
Spectroscopic Techniques ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pyridine Moiety ◽  
New Compounds

( E)-4-[2-(Pyridin-4-yl)vinyl]benzaldehyde, containing both a 4-vinylpyridine and an aldehyde functionality, is utilized to develop new, highly conjugated chalcone compounds and a bis-Schiff base azine compound. The chalcone-containing compounds are further explored for their protonation, methylation and silver(I) coordination chemistry using the pyridine moiety. In parallel, a cyano-containing analogue, ( E)-4-[2-(pyridin-4-yl)vinyl]benzonitrile is also synthesized and studied for its silver(I) coordination chemistry. These new compounds are fully characterized by mass spectrometry, elemental analysis and spectroscopic techniques. The methylated product of ( E)-1-(9-anthryl)-3-{4-[2-(pyridin-4-yl)vinyl]phenyl}prop-2-en-1-one and a silver complex of ( E)-4-[2-(pyridin-4-yl)vinyl]benzonitrile are structurally determined by X-ray crystallography.

scholarly journals A new one-pot three-component synthesis of 4-aryl-6-cycloamino-1,3,5-triazin-2-amines under microwave irradiation

Synthesis ◽  
2021 ◽  
Author(s):  
Muhammad Syafiq Bin Shahari ◽  
Ahmad Junaid ◽  
Edward R. T. Tiekink ◽  
Anton V. Dolzhenko
Keyword(s):  
Microwave Irradiation ◽  
Aromatic Aldehydes ◽  
Antileukemic Activity ◽  
One Pot ◽  
Biological Screening ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cyclic Amines ◽  
Three Component Reaction ◽  
Fast Synthesis

A new method for the fast synthesis of diverse 4-aryl-6-cycloamino-1,3,5-triazin-2-amines was developed. The synthesis is performed under microwave irradiation in a one-pot manner from cyanoguanidine, aromatic aldehydes, and cyclic amines. Their three-component reaction in the presence of hydrochloric acid produced dihydrotriazines, which were then converted (without isolation) to the targeted compounds via aromatic dehydrogenation in the presence of alkali. The reaction tolerated various aromatic aldehydes (including heterocyclic) and cyclic amines. Crystal structures of two representative 4-aryl-6-morpholino-1,3,5-triazin-2-amines were established by X-ray crystallography. The results of preliminary biological screening identified potent antileukemic activity for 6-(3,4-dihydroisoquinolin-2(1<i>H</i>)-yl)-4-phenyl-1,3,5-triazin-2-amine.

Zirconium complexes of a cyclopentadienyl-amido ligand with a pendant amine donor via amine and alkane elimination

1996 ◽  
Vol 74 (9) ◽  
pp. 1696-1703 ◽  
Author(s):  
Ying Mu ◽  
Warren E. Piers ◽  
Donald C. MacQuarrie ◽  
Michael J. Zaworotko
Keyword(s):  
Lewis Acids ◽  
Methyl Chloride ◽  
Monoclinic Space Group ◽  
One Pot ◽  
Amido Complexes ◽  
X Ray ◽  
X Ray Crystallography ◽  
Zirconium Complexes ◽  
Alkane Elimination

Zirconium complexes of the multidentate ligand CpHNMeSiN(H)R (SiNR = -SiMe2N-t-butyl; NMe = -CH2CH2NMe2, 1) were prepared and characterized via amine and alkane elimination procedures. Reaction of 1 with Zr(NMe2)4 gave a mixture of bis-amido complexes 2 in which the ligand was 1,2 and 1,3 substituted. This mixture was converted to the analogous dichlorides 3 using Me2NH•HCl and 1,3-3 was purified at this stage; alternatively, 1,3-3 was obtained in one pot from 1 and Zr(NMe2)4 in ≈70% yield. Conversion of 1,3-3 to dimethyl compound (CpNMeSiNR)Zr(CH3)2, 1,3-4, was accomplished via reaction of the dichloride with methyllithium; methide abstraction with the Lewis acids B(C6F5)3 and [Ph3C]+[B(C6F5)4]− generated the cationic alkyls [(CpNMeSiNR)Zr(CH3)]+[R′B(C6F5)3]− (R′ = CH3, 6a; C6F6, 6b), which were characterized by NMR spectroscopy. Zirconium complexes containing 1 ligated as its 1,2 isomer were obtained from alkane elimination reactions between 1 and in situ prepared RnZrCl4−n (R = CH3, n = 3; R = CH2SiMe3, n = 2). 1,2-3 and the methyl chloride complex 1,2-(CpNMeSiNR)Zr(CH3)Cl, 5, were obtained in 18 and 30% yield, respectively. Complex 5 was characterized by X-ray crystallography (monoclinic, space group P21/a, a = 9.6951(10) Å, b = 14.3794(16) Å, c = 14.364(3) Å, V = 1990.3(5) Å3, Z = 4, R = 0.046, Rw = 0.041.) Key words: amine elimination, Cp-amido, zirconium complexes.

Four coordination polymers based on dinuclear and trinuclear units with a new multifunctional pyridyl-dicarboxylate ligand: luminescence and magnetic properties

CrystEngComm ◽  
2017 ◽  
Vol 19 (38) ◽  
pp. 5755-5763 ◽  
Author(s):  
Feng Liu ◽  
Wei Gao ◽  
Xiu-Mei Zhang ◽  
Jie-Ping Liu ◽  
En-Qing Gao
Keyword(s):  
Magnetic Properties ◽  
Coordination Polymers ◽  
X Ray ◽  
X Ray Crystallography ◽  
Dicarboxylate Ligand ◽  
Solvothermal Conditions

Four coordination polymers with a new pyridyl-dicarboxylate ligand were synthesized under solvothermal conditions and studied by means of X-ray crystallography, topological analyses, luminescence and magnetic analyses.

Silane catecholates: versatile tools for self-assembled dynamic covalent bond chemistry

2019 ◽  
Vol 55 (43) ◽  
pp. 6066-6069 ◽  
Author(s):  
Yoshiteru Kawakami ◽  
Tsuyoshi Ogishima ◽  
Tomoki Kawara ◽  
Shota Yamauchi ◽  
Kazuhiko Okamoto ◽  
...  
Keyword(s):  
Covalent Bond ◽  
One Pot ◽  
X Ray ◽  
X Ray Crystallography ◽  
Self Assembled

Shape-persistent macrocycles and 3D nanocages have been prepared in one-pot under MeCN-promoted dynamic covalent bond conditions starting from silane catecholates, whose structures were confirmed by X-ray crystallography.

scholarly journals Reaction with Proteins of a Five-Coordinate Platinum(II) Compound

2019 ◽  
Vol 20 (3) ◽  
pp. 520 ◽  
Author(s):  
Giarita Ferraro ◽  
Tiziano Marzo ◽  
Maria Cucciolito ◽  
Francesco Ruffo ◽  
Luigi Messori ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Platinum Complexes ◽  
Rnase A ◽  
Side Chain ◽  
Planar Geometry ◽  
Ionization Mass ◽  
X Ray ◽  
X Ray Crystallography ◽  
Egg White Lysozyme ◽  
Square Planar

Stable five-coordinate Pt(II) complexes have been highlighted as a promising and original platform for the development of new cytotoxic drugs. Their interaction with proteins has been scarcely studied. Here, the reactivity of the five-coordinate Pt(II) compound [Pt(I)(Me) (dmphen)(olefin)] (Me = methyl, dmphen = 2,9-dimethyl-1,10-phenanthroline, olefin = dimethylfumarate) with the model proteins hen egg white lysozyme (HEWL) and bovine pancreatic ribonuclease (RNase A) has been investigated by X-ray crystallography and electrospray ionization mass spectrometry. The X-ray structures of the adducts of RNase A and HEWL with [Pt(I)(Me)(dmphen)(olefin)] are not of very high quality, but overall data indicate that, upon reaction with RNase A, the compound coordinates the side chain of His105 upon releasing the iodide ligand, but retains the pentacoordination. On the contrary, upon reaction with HEWL, the trigonal bi-pyramidal Pt geometry is lost, the iodide and the olefin ligands are released, and the metal center coordinates the side chain of His15 probably adopting a nearly square-planar geometry. This work underlines the importance of the combined use of crystallographic and mass spectrometry techniques to characterize, in detail, the protein–metallodrug recognition process. Our findings also suggest that five-coordinate Pt(II) complexes can act either retaining their uncommon structure or functioning as prodrugs, i.e., releasing square-planar platinum complexes as bioactive species.

Coordination Chemistry ofN,N,N′,N′-Tetraethylpyridine-2,6-dithiocarboxamide (S-dept) - X-ray Crystal Structures and Magnetic Properties of [Co(S-dept)X2] (X = Br, I, and NCS)

2005 ◽  
Vol 2005 (19) ◽  
pp. 3884-3893 ◽  
Author(s):  
Ramesh Kapoor ◽  
Ashok Kataria ◽  
Paloth Venugopalan ◽  
Pratibha Kapoor ◽  
Geeta Hundal ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Coordination Chemistry ◽  
Crystal Structures ◽  
X Ray

One-pot synthesis of 5-(8-ethoxycarbonyl-1-naphthyl)-10,15,20-triphenyl porphyrin (ENTPP) and spontaneous resolution upon crystallization

2011 ◽  
Vol 15 (03) ◽  
pp. 197-201 ◽  
Author(s):  
Juanxia Yang ◽  
Jiaxun Jiang ◽  
Weiguang Fang ◽  
Xiaoxu Kai ◽  
Chuanjiang Hu ◽  
...  
Keyword(s):  
Soret Band ◽  
Ester Group ◽  
Spontaneous Resolution ◽  
Cd Spectra ◽  
One Pot ◽  
Nmr Spectrum ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Entire Structure

5-(8-ethoxycarbonyl-1-naphthyl)-10,15,20-triphenyl porphyrin (ENTPP) has been synthesized in a one-pot reaction, and the corresponding chiral crystalline samples have been obtained by spontaneous resolution. 1 H NMR spectrum suggests it is mononaphthyl substituted species and an ethyl group is over the porphyrin plane. The structure has been further confirmed by X-ray crystallography. ENTPP·C6H14 (C57H50N4O2 ): monoclinic, P21, a = 10.707(2) Å, b = 12.203(2) Å, c = 17.858(4) Å, β = 103.06(3)°, V = 2272.8(8) Å3, Z = 2. The 8-position substituent, ester group, lies above the porphyrin plane and leads to the conformational chirality. The entire structure is built up with homochiral molecules, which leads to a chiral crystal through packing in P21 space group. Circular dichroism (CD) spectra have exhibited remarkable absorptions in the Soret band region, which further confirms the homochirality of the crystalline samples.

One-Dimensional Ag(I) Organometallic Coordination Polymers Generated from a Fulvene-Based Ligand

2006 ◽  
Vol 59 (3) ◽  
pp. 207 ◽  
Author(s):  
Peng Wang ◽  
Jian-Ping Ma ◽  
Ru-Qi Huang ◽  
Yu-Bin Dong
Keyword(s):  
Coordination Chemistry ◽  
Coordination Polymers ◽  
Chain Structure ◽  
One Pot ◽  
Trans Conformation ◽  
One Dimensional ◽  
X Ray ◽  
Triclinic System ◽  
Polymeric Complexes ◽  
Single Crystal Analysis

A new fulvene-based ligand L was synthesized and its coordination chemistry with Ag(i) ion has been investigated. Two novel Ag(i) polymeric complexes, [Ag2L2∙5.5(C6H6)]SbF6 (1) and [AgL∙2.5(C6H6)]SbF6 (2), were obtained by combination of L with AgSbF6 in one-pot reaction. X-Ray single-crystal analysis revealed that both 1 and 2 crystallize in triclinic system P1. In 1 and 2, the ligand L adopts a trans-conformation to bind the Ag(i) centres into a one-dimensional twin-chain structure through either Ag–O coordination or π–π interactions.

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