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.

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.

Metal Template Reactions. XXV. N-Acyl Isatin Precursors for the Synthesis of Malonamido Macrocyclic Metal Complexes

1987 ◽  
Vol 40 (10) ◽  
pp. 1745 ◽  
Author(s):  
DS Black ◽  
N Chaichit ◽  
BM Gatehouse ◽  
GI Moss
Keyword(s):  
Metal Complexes ◽  
Macrocyclic Complex ◽  
X Ray ◽  
X Ray Crystallography

Reaction of sodium isatide with dimethylmalonyl dichloride yielded the oxazinoindole (6) rather than the expected product (4). The glyoxylamide (8), which served as a precursor to the macrocyclic complex (15), was therefore prepared by a sequence involving compounds (9), (10) and (7). Such a route makes use of the reactivity of N-acyl isatins and the protecting capacity of the benzyloxycarbonyl group. The structure of compound (6) was established by X-ray crystallography.

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.

Bis-2-thienyldiethylaminophosphane as a Ligand in Late Transition Metal Complexes and its Transformation to Bis-2-thienylphosphane

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1429-1440
Author(s):  
Markus Granitzka ◽  
Peter Stollberg ◽  
Dietmar Stalke
Keyword(s):  
Nmr Spectroscopy ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Metal Salts ◽  
Inert Gas ◽  
Late Transition Metal ◽  
X Ray ◽  
Transition Metal Salts ◽  
Late Transition

Abstract Bis-2-thienyldiethylaminophosphane (C4H3S)2PNEt2 (1) is introduced as a ligand for late transition metal complexes ([(H3C4S)2PNEt2]nMXmLp), with M = Ni(II), Au(I), Cu(I), Pd(II), Ir(I), X = Cl, Br and L = NCMe, COD, (2-7). Reactions of 1 with the late transition metal salts NiCl2·dme, (Me2S)AuCl, CuCl, PdCl2(PhCN)2, and [Ir(COD)Cl]2 yield the complexes [{(H3C4S)2PNEt2}2 · NiCl2] (2), [(H3C4S)2PNEt2 · AuCl] (3) [(H3C4S)2PNEt2·CuCl(CH3CN)]2 (4), [{(H3C4S)2PNEt2}2 · PdCl2] (5), [{(H3C4S)2PNEt2}2·PdCl2]2 (6), and [(H3C4S)2PNEt2·IrCl(COD)] (7). In addition, the transformation of 1 to the valuable chlorine-substituted starting material (H3C4S)2PCl (8) and the related conversion of 8 to the secondary phosphane (H3C4S)2PH (9) is reported. The complexes 2-7 are stable under inert gas conditions and were characterized by single-crystal X-ray studies, NMR spectroscopy, and elemental analysis.

Synthesis and structure of isocorrole metal complexes

2009 ◽  
Vol 13 (02) ◽  
pp. 256-265 ◽  
Author(s):  
Jun-ichiro Setsune ◽  
Aki Tsukajima ◽  
Naho Okazaki
Keyword(s):  
Metal Complexes ◽  
Metal Coordination ◽  
Dinuclear Complexes ◽  
X Ray ◽  
X Ray Crystallography

gem-dimethylisocorrole gave four-coordinate Ni (II) and Cu (II) complexes, five-coordinate (chloro) Fe (III) and (chloro) Mn (III) complexes, and six-coordinate (chloro)(pyridinato) Rh (III) complex in moderate to good yields. The dinuclear complexes such as the μ-oxo-diiron(III) complex and tetracarbonyldirhodium(I) complex were also prepared. The structures of these mononuclear and dinuclear complexes were determined by X-ray crystallography. These structures are very similar to those of the corresponding metaloporphyrins but the presence of the sp3-meso carbon allows tilting of the pyrrole rings so as to adapt itself to various metal coordination geometries.

Metallkomplexe von biologisch wichtigen Liganden, CVI [1]. Metallkomplexe von Donor-substituierten Oxazolin-5-onen sowie von Bis(oxazolin-5-onen) / Metal Complexes of Biologically Important Ligands CVI [1], Metal Complexes of Donor Substituted Oxazolones and of Bis(oxazolones)

1998 ◽  
Vol 53 (9) ◽  
pp. 965-972 ◽  
Author(s):  
Markus Prem ◽  
Werner Bauer ◽  
Kurt Polbom ◽  
Wolfgang Beck
Keyword(s):  
Amino Acid ◽  
Metal Complexes ◽  
Nucleophilic Addition ◽  
Metal Salts ◽  
Amino Acid Esters ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
Close Proximity ◽  
Acid Esters

A series of chelate complexes 1-12 of Cu(II), Ni(II), Pd(II), and Ru(III) with the anion of 2-(2′-hydroxyphenyl)-5(4H)-oxazolone and with 2-(2′-aminophenyl)-5(4H)-oxazolone were prepared from metal salts or from chloro-bridged complexes [(R3P)MCl2]2 (M = Pd, Pt) and [(p-cymene)RuCl2]2. Nucleophilic addition of α-amino acid esters to the bis-chelate complexes M(oxophenyloxazolone)2(M = Ni, Cu) gave the dipeptide derivatives 13-18. Dinuclear Pd(II) and Pt(II) chelate complexes 19-23 were obtained from phenylene- and ethylenebridged bis(oxazolones). The structures of (Et3P)(Cl)Pd(O,N-oxophenyloxazolone) (6) and of Cl2(Et3P)Pt(2,2′-phenylene-bis(4-methyloxazolone)Pt(PEt3)Cl2 (20) were determined by X-ray diffraction. In complex 20 a close proximity of two phenylene H atoms to the metal is observed.

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