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 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’.

Synthesis, structural characterization, and reactivity of late transition-metal complexes bearing linked cyclopentadienyl–carboranyl ligands

2012 ◽  
Vol 90 (1) ◽  
pp. 108-117 ◽  
Author(s):  
Dongmei Liu ◽  
Zaozao Qiu ◽  
Hoi-Shan Chan ◽  
Zuowei Xie
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Structural Characterization ◽  
Molecular Structures ◽  
Spectroscopic Techniques ◽  
Late Transition Metal ◽  
X Ray ◽  
Elemental Analyses ◽  
Late Transition

Late transition-metal complexes bearing linked cyclopentadienyl/indenyl–carboranyl ligands were synthesized and their reactivities were examined. Reaction of Li2[Me2C(L)(C2B10H10)] (L = C5H4, C9H6, Me2NCH2CH2C5H3) with MCl2(PPh3)2 in Et2O afforded [η5:σ-Me2C(C5H4)(C2B10H10)]M(PPh3) (M = Co (4), Ni (5)), [η5:σ-Me2C(C9H6)(C2B10H10)]M(PPh3) (M = Co (6), Ni (7)), and [η5:σ-Me2C(Me2NCH2CH2C5H3)(C2B10H10)]Ni(PPh3) (8). Treatment of 4 or 5 with 2,6-dimethylphenylisocyanide, N-heterocyclic carbene (NHC), PCy3, or 1,2-bis(diphenylphosphino)ethane (dppe) gave the corresponding PPh3 displacement complexes [η5:σ-Me2C(C5H4)(C2B10H10)]M(2,6-Me2C6H3NC) (M = Co (9), Ni (10)), [η5:σ-Me2C(C5H4)(C2B10H10)]M[1,3-(2,6-i-Pr2C6H3)2C3N2H2] (M = Co (11), Ni (12)), [η5:σ-Me2C(C5H4)(C2B10H10)]Ni(PCy3) (13), or {[η5:σ-Me2C(C5H4)(C2B10H10)]Co}2(dppe) (14), respectively. These complexes were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 4–14 were further confirmed by single-crystal X-ray analyses.

Syntheses and Structure Investigations of 3d Transition Metal Complexes with a Flexible N4O2-Donor Hexadentate Schiff-Base Ligand

2017 ◽  
Vol 70 (5) ◽  
pp. 581 ◽  
Author(s):  
Kyle J. Howard-Smith ◽  
Alexander R. Craze ◽  
Mohan Badbhade ◽  
Christopher E. Marjo ◽  
Timothy D. Murphy ◽  
...  
Keyword(s):  
Schiff Base ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Schiff Base Ligand ◽  
High Resolution Mass Spectrometry ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structure Investigations

The syntheses and structure investigations of four new 3d transition metal complexes (1–4) with a flexible N4O2-donor hexadentate Schiff-base ligand are described; three complexes (1, 2, and 4) of FeIII, CoIII, and CuII metal ions have been investigated by UV-vis, FT-IR, high-resolution mass spectrometry (HR-MS), and scanning electron microscopy–electron dispersive spectroscopy, as well as single crystal X-ray diffraction. The X-ray structure of NiII complex 3 is also reported. The molecular structures of the complexes (1–3) demonstrate distorted octahedral coordination geometry, each exhibiting 1 : 1 (M : L) ratios and the CuII complex 4 shows a trinuclear structure with a CuII : L ratio of 3 : 2 in the solid state, which has been proven by X-ray diffraction. On the other hand, a mononuclear species of the CuII complex is formed in solution, which has been identified by electrospray ionization HR-MS.

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 Azoligands as Bridged in Macrocyclic Dinickel Complexes

2010 ◽  
Vol 5 (1) ◽  
pp. 7-23
Author(s):  
Vasile Lozan
Keyword(s):  
Coordination Chemistry ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
X Ray ◽  
X Ray Crystallography ◽  
Coordination Site ◽  
Wide Range

The coordination chemistry of dinickel macrocyclic hexaamine-dithiophenolate complexes of Robson-type with azoligands is presented in this microreview. All complexes have been characterised by IR-,UV/Visspectroscopy, and X-ray crystallography. The bioctahedral transition metal complexes of the type [(L6)Ni2(μ-L')]+ exhibit a rich coordination chemistry since the active coordination site L' is accessible for a wide range of exogenous coligands.

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.

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

scholarly journals 1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1390 ◽  
Author(s):  
Ilya G. Shenderovich
Keyword(s):  
Chemical Shift ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Density Functional ◽  
Molecular Structures ◽  
Basis Sets ◽  
Functional Theory ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its 31P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this 31P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported.

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