scholarly journals A New Tetradentate Mixed Aza-Thioether Macrocycle and Its Complexation Behavior towards Fe(II), Ni(II) and Cu(II) Ions

Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2030 ◽  
Author(s):  
Sze-Wing Ng ◽  
Siu-Chung Chan ◽  
Chi-Fung Yeung ◽  
Shek-Man Yiu ◽  
Chun-Yuen Wong
Keyword(s):  
Metal Complexes ◽  
Macrocyclic Ligand ◽  
Tetradentate Ligand ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Precursors

A new tetradentate mixed aza-thioether macrocyclic ligand 2,6-dithia[7](2,9)-1,10-phenanthrolinophane ([13]ane(phenN2)S2) was successfully synthesized. Reacting metal precursors [Fe(CH3CN)2(OTf)2], Ni(ClO4)2·6H2O, and Cu(ClO4)2·6H2O with one equivalent of [13]ane(phenN2)S2 afforded [Fe([13]ane(phenN2)S2)(OTf)2] (1), [Ni([13]ane(phenN2)S2)](ClO4)2 (2(ClO4)2), and [Cu([13]ane(phenN2)S2)(OH2)](ClO4)2 (3(ClO4)2), respectively. The structures of [13]ane(phenN2)S2 and all of its metal complexes were investigated by X-ray crystallography. The [13]ane(phenN2)S2 was found to behave as a tetradentate ligand via its donor atoms N and S.

Two Metal Complexes of the Macrocyclic Ligand 1,4,7-Triazacyclodecane (tacd). Crystal Structures of [Zn(tacd)2](ClO4)2 and [Cu(tacd)2]Br2.4H2O

1995 ◽  
Vol 48 (1) ◽  
pp. 139 ◽  
Author(s):  
XM Chen ◽  
YX Yao ◽  
KL Shi ◽  
TCW Mak
Keyword(s):  
Metal Complexes ◽  
Crystal Structures ◽  
Macrocyclic Ligand ◽  
Octahedral Coordination ◽  
Coordination Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Distorted Octahedral

Two metal complexes of 1,4,7-triazacyclodecane ( tacd ), [Zn( tacd )2] (ClO4)2 (1) and [Cu( tacd )2] Br2.4H2O (2), have been prepared and characterized by X-ray crystallography. Crystals of (1) are monoclinic, P21/n, a 9.506(2), b 10.279(3), c 11.505(2) Ǻ, β 91.29(2)°; crystals of (2) are orthorhombic, Pbca, a 12.035(3), b 13.673(3), c 14.248(2) Ǻ. The zinc(II) atom in (1) is surrounded in a distorted octahedral N6 environment with Zn-N bonds at 2.121(5)-2.131(4) Ǻ; the copper(II) atom in (2) adopts an elongated octahedral coordination geometry with the Cu-N bonds at 2.066(4)-2.294(5) Ǻ.

Simultaneous Generation of a [2×2] Grid-like Complex and a Linear Double Helicate: A Three-Level Self-Sorting Process

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn ◽  
Corinne Bailly ◽  
Lydia Karmazin
Keyword(s):  
Metal Complexes ◽  
Mass Spectroscopy ◽  
Metal Salts ◽  
Simultaneous Generation ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sorting Process

<div>Two constitutional dynamic libraries (CDLs)—each containing two amines, two dialdehydes and two metal salts—have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures sharing no component, a [2×2] grid-like complex and a linear double helicate. These CDLs provided unique examples of a three-level self-sorting process, as only two imine-based ligand constituents, two metal complexes and two architectures were selected during their assembling out of all the possible combinations of their initial components. The metallosupramolecular architectures assembled were characterized by NMR, mass spectroscopy, and X-ray crystallography.</div>

scholarly journals Simultaneous Generation of a [2×2] Grid-like Complex and a Linear Double Helicate: A Three-Level Self-Sorting Process

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn ◽  
Corinne Bailly ◽  
Lydia Karmazin
Keyword(s):  
Metal Complexes ◽  
Mass Spectroscopy ◽  
Metal Salts ◽  
Simultaneous Generation ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sorting Process

<div>Two constitutional dynamic libraries (CDLs)—each containing two amines, two dialdehydes and two metal salts—have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures sharing no component, a [2×2] grid-like complex and a linear double helicate. These CDLs provided unique examples of a three-level self-sorting process, as only two imine-based ligand constituents, two metal complexes and two architectures were selected during their assembling out of all the possible combinations of their initial components. The metallosupramolecular architectures assembled were characterized by NMR, mass spectroscopy, and X-ray crystallography.</div>

scholarly journals Characterization of reactive organometallic species via MicroED

2019 ◽  
Author(s):  
Christopher Jones ◽  
Matthew Asay ◽  
Lee Joon Kim ◽  
Jack Kleinsasser ◽  
Ambarneil Saha ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Cryogenic Cooling ◽  
Structural Determination ◽  
X Ray ◽  
X Ray Crystallography ◽  
Diamagnetic Transition

Here we apply microcrystal electron diffraction (MicroED) to the structural determination of transition metal complexes. We find that the simultaneous use of 300 keV electrons, very low electron doses, and an ultra-sensitive camera allows for the collection of data without cryogenic cooling of the stage. This technique reveals the first crystal structures of the classic zirconocene hydride, colloquially known as “Schwartz’s reagent”, a novel Pd(II) complex not amenable to solution-state NMR or X-ray crystallography, and five other paramagnetic or diamagnetic transition metal complexes.

scholarly journals X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

2017 ◽  
Vol 375 (2084) ◽  
pp. 20160028 ◽  
Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Metal Organic Frameworks ◽  
Void Space ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Nitrates ◽  
Metal Organic

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

Übergangsmetallkomplexe mit Schwefelliganden, LXXIII. Diastereospezifische Dichlormethylierung schwefelreicher [RuII(SRR′)(PPh3)′S4]-Komplexe (SRR′ = einzähniger Thioether- oder Thiol-Ligand; ′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, LXXIII. Diastereospecific Dichloromethylation of Sulfur Rich [RuII(SRR′)(PPh3)′S4] Complexes (SRR′ = Monodentate Thioether or Thiol Ligand;′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))

1991 ◽  
Vol 46 (12) ◽  
pp. 1585-1592 ◽  
Author(s):  
Dieter Sellmann ◽  
Peter Lechner ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Structures ◽  
X Ray ◽  
X Ray Crystallography ◽  
Thiol Ligand

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.

Coordination chemistry of thioether–pyridazine macrocycles. III. Synthetic, structural, and spectroscopic studies of Cu(II), Cu(II)Cu(I), and Cu(I) complexes of a hexathiapyridazinophane macrocyclic ligand

1993 ◽  
Vol 71 (7) ◽  
pp. 1086-1093 ◽  
Author(s):  
Liqin Chen ◽  
Laurence K. Thompson ◽  
John N. Bridson
Keyword(s):  
Mass Spectrometry ◽  
Macrocyclic Ligand ◽  
Spectroscopic Studies ◽  
Orthorhombic System ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Triclinic System ◽  
Square Planar ◽  
Copper Centre

The preparation and properties of the thioether–pyridazine macrocycle (L4; C16H20S6N4) containing two pyridazine subunits, and its Cu(II), Cu(II)Cu(I), and Cu(I) complexes are described. The ligand is characterized by 1H nuclear magnetic resonance and mass spectrometry, and the complexes by infrared, eleetronic spectra, and magnetism, and in some cases by X-ray crystallography. The complex [Cu2(L4)Cl4]x, (1) crystallized in the triclinic system, space group [Formula: see text] with a = 8.6204(8) Å, b = 9.850(1) Å, c = 8.348(1) Å, α = 111.46(1)°, β = 102.50(1)°, γ = 71.818(9)°, V = 622.6(1) Å3, and Z = 1 (R = 0.043, Rw = 0.042 for 1312 reflections). Two monodentate pyridazine rings in the same ligand bind to one trans square-planar copper centre (CuN2Cl2) with two sulfurs from each ligand binding to another trans square-planar copper centre (CuS2Cl2) to form a polynuclear chain. The complex [Cu(L4)Cl2] (3) crystallized in the triclinic system, space group [Formula: see text] with a = 11.001(1) Å, b = 12.888(2) Å, c = 8.704(1) Å, α = 102.89(1)°, β = 103.36(1)°,γ = 75.84(1)°, V = 1145.8(3) Å3 and Z = 2 (R = 0.056, Rw = 0.044 for 2059 reflections). A trans square-planar structure (CuN2Cl2) exists for 3 with monodentate pyridazines. [Cu(L4)(NO3)2] (4) crystallized in the orthorhombic system, space group P212121, with a = 15.148(2) Å, b = 15.562(3) Å, c = 11.064(1) Å, V = 2608.2(7) Å3 and Z = 4 (R = 0.039, Rw = 0.034 for 1864 reflections). Two monodentate pyridazine rings and two bidentate nitrates bind to a pseudo-octahedral copper(II) centre.

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