Trianionic binucleating bis(trityl)/aryloxide ligands and their lithium, magnesium, and zinc complexes

2020 ◽  
Vol 98 (8) ◽  
pp. 453-459
Author(s):  
Tingshan Zhong ◽  
Jixing Zhao ◽  
Hao Lei
Keyword(s):  
Infrared Spectroscopy ◽  
Metal Complexes ◽  
Zinc Complexes ◽  
Electrochemical Methods ◽  
Redox Property ◽  
Metal Centers ◽  
X Ray ◽  
X Ray Crystallography ◽  
Lithium Complexes

A series of lithium complexes with trianionic bis(trityl)/aryloxide ligands were prepared by triple deprotonation of phenols with two ortho-diarylmethyl substituents. Transmetalation with one of the lithium complexes via salt metathesis resulted in the synthesis of corresponding Mg and Zn complexes, which showed distinct coordination stoichiometry and structures. The metal complexes were characterized by multi-nuclear NMR, UV–vis, and infrared spectroscopy. Additionally, the redox property of a trilithium compound was investigated by electrochemical methods. X-ray crystallography revealed that the new bis(trityl)/aryloxide ligands could simultaneously bind to two nearby metal centers both in chelating κ2-O,C fashion, making themselves rare examples of tridentate binucleating alkyl/aryloxo scaffolds.

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>

Synthesis, Characterisation and Structural Studies of [Zn(phen)3][Fe(CN)5(NO)]·2H2O·0.25MeOH and [(bipy)2(H2O)Zn(μ-NC)Fe(CN)4(NO)]·0.5H2O

2003 ◽  
Vol 58 (9) ◽  
pp. 916-921 ◽  
Author(s):  
Amitabha Datta ◽  
Samiran Mitra ◽  
Georgina Rosair
Keyword(s):  
Infrared Spectroscopy ◽  
Thermogravimetric Analysis ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Structural Studies ◽  
Crystal Lattices ◽  
X Ray ◽  
X Ray Crystallography ◽  
Distorted Octahedral ◽  
Solvent Molecules

Two new bimetallic complexes [Zn(phen)3][Fe(CN)5(NO)] · 2 H2O · 0.25 MeOH, (1) and [(bipy)2(H2O)Zn(μ-NC)Fe(CN)4(NO)] · 0.5 H2O, (2), have been isolated (where phen = 1,10-phenanthroline and bipy = bipyridyl) and characterised by X-ray crystallography [as the 2 H2O · 0.25 CH3OH solvate for (1) and hemihydrate for (2)] infrared spectroscopy and thermogravimetric analysis. Substitution of phenanthroline for bipyridyl resulted in a cyano-bridged bimetallic species rather than two discrete mononuclear metal complexes. The bond angles of Fe-N-O were shown to be practically linear for both 1 [179.2(7)°] and 2 [178.3(3)°], and the Zn atoms have distorted octahedral geometry. The solvent molecules in both crystal lattices take part in forming hydrogen-bonded networks.

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’.

scholarly journals Thermal, spectroscopic, X-ray and theoretical studies of metal complexes (sodium, manganese, copper, nickel, cobalt and zinc) with pyrimidine-5-carboxylic and pyrimidine-2-carboxylic acids

2019 ◽  
Vol 138 (4) ◽  
pp. 2813-2837 ◽  
Author(s):  
G. Świderski ◽  
R. Świsłocka ◽  
R. Łyszczek ◽  
S. Wojtulewski ◽  
M. Samsonowicz ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Nitrogen Atom ◽  
Metal Complexes ◽  
General Formula ◽  
Pyrimidine Ring ◽  
Carboxylate Ligand ◽  
Metal Centers ◽  
X Ray ◽  
Carboxylate Oxygen ◽  
3D Metal Complexes

Abstract The new 3d metal complexes of pyrimidine-2-carboxylic (2PCA) and pyrimidine-5-carboxylic (5PCA) acids were synthesized and characterized using thermal analysis (TG–DSC, TG–FTIR), X-ray, spectroscopic (IR, Raman) methods and theoretical (DFT) studies. In the complexes of pyrimidine-2-carboxylic acid of the general formula M(2PCA)2·xH2O (where 2PCA-pyrimidine-2-carboxylate; M = Mn(II), Co(II), Ni(II), Cu(II) and Zn; x = 0 for Mn and Cu; x = 2 for Co, Ni and Zn) coordination of metal ions occurs through nitrogen atom from pyrimidine ring and carboxylate oxygen atom. The complexes of pyrimidine-5-carboxylic acid of the general formula M(5PCA)2·xH2O (where 5PCA—pyrimidine-5-carboxylate; M = Mn(II), Co(II), Ni(II), Cu(II) and Zn; x = 6 for Cu and 4 for remaining complexes) were obtained as monomeric isostructural compounds. Coordination of metal centers occurs through two nitrogen atom from different pyrimidine-5-carboxylate ligand and four oxygen atoms from water molecules. The IR and Raman spectra of free acids as well as obtained metal(II) complexes were described in detail. Aromaticity (HOMA, EN, GEO and I6) of complexes was determined and discussed. The investigated compounds decompose in air in two main stages connected with dehydration and decomposition/burning of anhydrous compounds to the suitable metal oxides. Thermal decomposition in nitrogen leads to the evolution of water, carbon oxides, ammonia and pyrimidine molecules.

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.

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.

Synthesis, characterization, crystal structure, electrochemical, solvatochromic and biological investigation of novel N4 and N3 type Cu(ii) Schiff base complexes

2017 ◽  
Vol 41 (21) ◽  
pp. 12554-12561 ◽  
Author(s):  
Akbar Azary ◽  
Abolfazl Bezaatpour ◽  
Saber Zahri ◽  
Mandana Amiri
Keyword(s):  
Crystal Structure ◽  
Schiff Base ◽  
Infrared Spectroscopy ◽  
Elemental Analysis ◽  
Schiff Base Complexes ◽  
Conductivity Measurements ◽  
Biological Investigation ◽  
X Ray ◽  
X Ray Crystallography

In the present study, three novel Cu(ii) Schiff base complexes were synthesized and characterized using infrared spectroscopy, elemental analysis, conductivity measurements and X-ray crystallography.

Übergangsmetallkomplexe mit Schwefelliganden, XXXII*: Synthese der sterisch anspruchsvollen Thiolat-amin-Liganden tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethan sowie ihrer Eisen-, Ruthenium- und Zink-Komplexe [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] und [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3/ Transition Metal Complexes with Sulfur Ligands, XXXII*: Synthesis of the Sterically Demanding New Thiolate-amine Ligands tbu2-ma-H = 2-Mercapto-3,5-di-tbutylanilin und tbu4-bmae-H2 = 1,2-Bis(2-mercapto-3,5-di-tbutylaniIino)ethane as well as of their Iron-, Ruthenium- and Zinc Complexes [Fe(CO)2(tbu2-ma)2], [Zn(tbu2-ma)2] and [RuL2(tbu4-bmae)], L = CO, PMe3, PPh3

1987 ◽  
Vol 42 (10) ◽  
pp. 1291-1297 ◽  
Author(s):  
Dieter Sellmann ◽  
Olaf Käppler
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Acid Hydrolysis ◽  
Organic Solvents ◽  
Transition Metal Complexes ◽  
Zinc Complexes ◽  
Metal Centers ◽  
Sterically Demanding ◽  
Amine Ligands ◽  
Soluble Complexes

Abstract In order to obtain soluble complexes containing sterically protected metal centers the new bi- and tetradentate thiolate amine ligands 2-mercapto-3,5-di-tbutylaniline (= tbu2-ma-H) and 1,2-bis(2-mercapto-3,5-di-tbutylanilino)ethane (= tbu4-mae-H2) were synthesized. tbu2-ma-H reacts with FeCl2-4 H2O and CO to give [Fe(CO)2(tbu2-ma)2], with Zn(ac)2 -2 H2O [Zn(tbu2-ma)2] is obtained whose acid hydrolysis and reaction with H2S, respectively, yield pure tbu2-Ina-H. The condensation of tbu2-ma-H with glyoxal yields the respective bis-benzthiazolidine, which is re­duced by LiAlH4 in the presence of Na[N(SiMe3)2] to tbu4-bmae-H2. tbu4-bmae-Li2. reacts with [Ru(CO)3(THF)Cl2], [Ru(PMe3)4Cl2] and [Ru(PPh3)2(CH3CN)2Cl2], respectively, to yield [Ru(L)2(Tm4-bmae)j (L = CO, PMe3, PPh3). The complexes are more soluble in organic solvents than the corresponding unsubstituted bmae complexes, bmae2- = 1,2-bis(2-mercaptoanilino)- ethane(2-).

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