scholarly journals An Isolable Mononuclear Palladium(I) Amido Complex

2021 ◽  
Author(s):  
jian Liu ◽  
Melissa Bollmeyer ◽  
Yujeong Kim ◽  
Dengmengfei Xiao ◽  
Samantha N. Macmillan ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Bond Cleavage ◽  
Primary Amines ◽  
Dispersion Force ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pauli Repulsion ◽  
Catalyzed Reactions ◽  
Electron Paramagnetic

Mononuclear Pd(I) species are putative intermediates in Pd-catalyzed reactions, but our knowledge about them is limited due to difficulties in accessing them. Herein, we report the isolation of a Pd(I) amido complex, [(BINAP)Pd(NHArTrip )] (BINAP = 2,2′- bis(diphenylphosphino)-1,1′-binaphthalene, ArTrip = 2,6-bis(2’,4’,6’-triisopropylphenyl)phenyl), from the reaction of (BINAP)PdCl2 with LiNHArTrip. This Pd(I) amido species has been characterized by X-ray crystallography, electron paramagnetic resonance, and multi-edge Pd Xray absorption spectroscopy. Theoretical study revealed that, while the 3-electron-2-center π interaction between Pd and N in the Pd(I) complex imposes severe Pauli repulsion in its Pd–N bond, pronounced attractive inter-ligand dispersion force aids its stabilization. In accord with its electronic features, reactions of homolytic Pd–N bond cleavage and deprotonation of primary amines are observed on the Pd(I) amido complex.

scholarly journals An Isolable Mononuclear Palladium(I) Amido Complex

2021 ◽  
Author(s):  
jian Liu ◽  
Melissa Bollmeyer ◽  
Yujeong Kim ◽  
Dengmengfei Xiao ◽  
Samantha N. Macmillan ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Bond Cleavage ◽  
Primary Amines ◽  
Dispersion Force ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pauli Repulsion ◽  
Catalyzed Reactions ◽  
Electron Paramagnetic

Mononuclear Pd(I) species are putative intermediates in Pd-catalyzed reactions, but our knowledge about them is limited due to difficulties in accessing them. Herein, we report the isolation of a Pd(I) amido complex, [(BINAP)Pd(NHArTrip )] (BINAP = 2,2′- bis(diphenylphosphino)-1,1′-binaphthalene, ArTrip = 2,6-bis(2’,4’,6’-triisopropylphenyl)phenyl), from the reaction of (BINAP)PdCl2 with LiNHArTrip. This Pd(I) amido species has been characterized by X-ray crystallography, electron paramagnetic resonance, and multi-edge Pd Xray absorption spectroscopy. Theoretical study revealed that, while the 3-electron-2-center π interaction between Pd and N in the Pd(I) complex imposes severe Pauli repulsion in its Pd–N bond, pronounced attractive inter-ligand dispersion force aids its stabilization. In accord with its electronic features, reactions of homolytic Pd–N bond cleavage and deprotonation of primary amines are observed on the Pd(I) amido complex.

scholarly journals Extending electron paramagnetic resonance to nanoliter volume protein single crystals using a self-resonant microhelix

2019 ◽  
Vol 5 (10) ◽  
pp. eaay1394 ◽  
Author(s):  
Jason W. Sidabras ◽  
Jifu Duan ◽  
Martin Winkler ◽  
Thomas Happe ◽  
Rana Hussein ◽  
...  
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Single Crystals ◽  
Active Site ◽  
Measured Signal ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
X Ray Crystallography ◽  
X Band ◽  
Electron Paramagnetic ◽  
Epr Experiments

Electron paramagnetic resonance (EPR) spectroscopy on protein single crystals is the ultimate method for determining the electronic structure of paramagnetic intermediates at the active site of an enzyme and relating the magnetic tensor to a molecular structure. However, crystals of dimensions typical for protein crystallography (0.05 to 0.3mm) provide insufficient signal intensity. In this work, we present a microwave self-resonant microhelix for nanoliter samples that can be implemented in a commercial X-band (9.5 GHz) EPR spectrometer. The self-resonant microhelix provides a measured signal-to-noise improvement up to a factor of 28 with respect to commercial EPR resonators. This work opens up the possibility to use advanced EPR techniques for studying protein single crystals of dimensions typical for x-ray crystallography. The technique is demonstrated by EPR experiments on single crystal [FeFe]-hydrogenase (Clostridium pasteurianum; CpI) with dimensions of 0.3 mm by 0.1 mm by 0.1 mm, yielding a proposed g-tensor orientation of the Hox state.

The neutral complex [CrIII4(μ3-O)2(μ2-CH3CO2)7(tbpy0)(tbpy•)]0 — a tetranuclear Cr(III) species containing a neutral (bpy0) and a π-radical anion (bpy•)1–

2014 ◽  
Vol 92 (10) ◽  
pp. 913-917 ◽  
Author(s):  
Mei Wang ◽  
Eckhard Bill ◽  
Thomas Weyhermüller ◽  
Karl Wieghardt
Keyword(s):  
Quantum Interference ◽  
Radical Anion ◽  
Resonance Spectrum ◽  
Coupling Model ◽  
Superconducting Quantum Interference Device ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
X Ray Crystallography ◽  
X Band ◽  
Electron Paramagnetic

The tetranuclear neutral species [CrIII4(μ3-O)2(μ2-CH3CO2)7(tbpy0)(tbpy•)]0·3THF has been prepared from a mixture of [CrII2(μ2-CH3CO2)4]·2H2O and 4,4′-di-tert-butyl-2,2′-bipyridine (1:2) in tetrahydrofuran (THF) under anaerobic conditions. Black crystals of [CrIII4(μ-O)2(μ-CH3CO2)7(tbpy)2]0 were grown and investigated by X-ray crystallography: a [Cr4O2]8+ butterfly core structure has been identified. In addition, the presence of seven μ2-acetate bridges, a neutral (tbpy0) ligand, and a single π-radical anion (tbpy•)1– have been clearly identified. The magnetic properties have been investigated by solid-state SQUID (superconducting quantum interference device) measurements (2–300 K) and a coupling model is presented. Its X-band electron paramagnetic resonance spectrum has been recorded at 10 and 300 K in toluene solution and successfully simulated. The spin of the (tbpy•)1– radical couples strongly antiferromagnetically to one Cr(III) center (J4 = –129 cm−1). These properties are compared with those reported previously for the monocationic species [CrIII4(μ3-O)2(μ2-CH3CO2)7(bpy0)2](PF6) in Bino et al. (Inorg. Chem. 1991, 30, 856).

scholarly journals Geometric and electronic structure of a peroxomanganese(iii) complex supported by a scorpionate ligand

2014 ◽  
Vol 43 (48) ◽  
pp. 17949-17963 ◽  
Author(s):  
Hannah E. Colmer ◽  
Robert A. Geiger ◽  
Domenick F. Leto ◽  
Gayan B. Wijeratne ◽  
Victor W. Day ◽  
...  
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Electronic Structure ◽  
Magnetic Circular Dichroism ◽  
Paramagnetic Resonance ◽  
X Ray ◽  
X Ray Crystallography ◽  
Magnetic Circular Dichroism Spectroscopy ◽  
Electron Paramagnetic ◽  
Circular Dichroïsm ◽  
Scorpionate Ligand

A peroxomanganese(iii) species with a scorpionate (Tp) ligand is characterized by X-ray crystallography, electron paramagnetic resonance, and magnetic circular dichroism spectroscopy, revealing a distinct electronic structure.

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