scholarly journals DFT-D4 Counterparts of Leading Meta-GGA and Hybrid Density Functionals for Energetics and Geometries

2020 ◽  
Author(s):  
Asim Najibi ◽  
LARS GOERIGK
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Complex Geometries ◽  
Density Functionals ◽  
Metal Organic ◽  
Reaction Energies ◽  
Cost Efficient

<div> <div> <div> <p>Previously, we introduced DFT-D3(BJ) variants of the B97M-V, ωB97X-V and ωB97M-V functionals and assessed them for the GMTKN55 database [Najibi and Go- erigk, <i>J Chem. Theory Comput.</i> <b>2018</b>, <i>14</i>, 5725]. In this study, we present DFT-D4 damping parameters to build the DFT-D4 counterparts of these functionals and assess these in comparison. We extend our analysis beyond GMTKN55 and especially turn our attention to enzymatically catalysed and metal-organic reactions. We find that B97M-D4 is now the second-best performing meta-GGA functional for the GMTKN55 database and it can provide noticeably better organometallic reaction energies com- pared to B97M-D3(BJ). Moreover, the aforementioned DFT-D3(BJ) based functionals have not been thoroughly assessed for geometries and herein we close this gap by analysing geometries of noncovalently bound dimers and trimers, peptide conformers, water hexamers and transition-metal complexes. We find that several of the B97(M)- based methods—particularly the DFT-D4 versions—surpass the accuracy of previously studied methods for peptide conformer, water hexamer, and transition-metal complex geometries, making them safe-to-use, cost-efficient alternatives to the original methods. The DFT-D4 variants can be easily used with ORCA4.1 and above. </p> </div> </div> </div>

scholarly journals DFT-D4 Counterparts of Leading Meta-GGA and Hybrid Density Functionals for Energetics and Geometries

2020 ◽  
Author(s):  
Asim Najibi ◽  
LARS GOERIGK
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Complex Geometries ◽  
Density Functionals ◽  
Metal Organic ◽  
Reaction Energies ◽  
Cost Efficient

<div> <div> <div> <p>Previously, we introduced DFT-D3(BJ) variants of the B97M-V, ωB97X-V and ωB97M-V functionals and assessed them for the GMTKN55 database [Najibi and Go- erigk, <i>J Chem. Theory Comput.</i> <b>2018</b>, <i>14</i>, 5725]. In this study, we present DFT-D4 damping parameters to build the DFT-D4 counterparts of these functionals and assess these in comparison. We extend our analysis beyond GMTKN55 and especially turn our attention to enzymatically catalysed and metal-organic reactions. We find that B97M-D4 is now the second-best performing meta-GGA functional for the GMTKN55 database and it can provide noticeably better organometallic reaction energies com- pared to B97M-D3(BJ). Moreover, the aforementioned DFT-D3(BJ) based functionals have not been thoroughly assessed for geometries and herein we close this gap by analysing geometries of noncovalently bound dimers and trimers, peptide conformers, water hexamers and transition-metal complexes. We find that several of the B97(M)- based methods—particularly the DFT-D4 versions—surpass the accuracy of previously studied methods for peptide conformer, water hexamer, and transition-metal complex geometries, making them safe-to-use, cost-efficient alternatives to the original methods. The DFT-D4 variants can be easily used with ORCA4.1 and above. </p> </div> </div> </div>

scholarly journals DFT-D4 Counterparts of Leading Meta-GGA and Hybrid Density Functionals for Energetics and Geometries

2020 ◽  
Author(s):  
Asim Najibi ◽  
LARS GOERIGK
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Complex Geometries ◽  
Density Functionals ◽  
Metal Organic ◽  
Reaction Energies ◽  
Cost Efficient

<div> <div> <div> <p>Previously, we introduced DFT-D3(BJ) variants of the B97M-V, ωB97X-V and ωB97M-V functionals and assessed them for the GMTKN55 database [Najibi and Go- erigk, <i>J Chem. Theory Comput.</i> <b>2018</b>, <i>14</i>, 5725]. In this study, we present DFT-D4 damping parameters to build the DFT-D4 counterparts of these functionals and assess these in comparison. We extend our analysis beyond GMTKN55 and especially turn our attention to enzymatically catalysed and metal-organic reactions. We find that B97M-D4 is now the second-best performing meta-GGA functional for the GMTKN55 database and it can provide noticeably better organometallic reaction energies com- pared to B97M-D3(BJ). Moreover, the aforementioned DFT-D3(BJ) based functionals have not been thoroughly assessed for geometries and herein we close this gap by analysing geometries of noncovalently bound dimers and trimers, peptide conformers, water hexamers and transition-metal complexes. We find that several of the B97(M)- based methods—particularly the DFT-D4 versions—surpass the accuracy of previously studied methods for peptide conformer, water hexamer, and transition-metal complex geometries, making them safe-to-use, cost-efficient alternatives to the original methods. The DFT-D4 variants can be easily used with ORCA4.1 and above. </p> </div> </div> </div>

Transition Metal Complex Catalysed Photo- and Electrochemical (De)hydrogenations Involving C=O- and C=N-Bonds

Synthesis ◽  
2021 ◽  
Author(s):  
Igor Fokin ◽  
Kai-Thorben Kuessner ◽  
Inke Siewert
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Basic Principles

Herein, we summarize the photo- and electrochemical protocols for dehydrogenation and hydrogenations involving carbonyl and imine functions. The three basic principles that have been explored to interconvert such moieties with transition metal complexes are discussed in detail and the substrate scope is evaluated. Furthermore, we describe some general thermodynamic and kinetic aspects of such electro- and photochemically driven reactions.

scholarly journals Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes

2020 ◽  
Vol 11 (36) ◽  
pp. 9836-9851
Author(s):  
Katherine J. Lee ◽  
Kunal M. Lodaya ◽  
Cole T. Gruninger ◽  
Eric S. Rountree ◽  
Jillian L. Dempsey
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Redox Mediators ◽  
Insoluble Material ◽  
Molecular Transition ◽  
Novel Strategy

We present an example of electrochemically-driven solubility cycling of a molecular transition metal complex and report a novel strategy for catalytically enhancing the oxidation of an insoluble material using homogeneous redox mediators.

scholarly journals Resolving structures of transition metal complex reaction intermediates with femtosecond EXAFS

2020 ◽  
Vol 22 (5) ◽  
pp. 2660-2666 ◽  
Author(s):  
Alexander Britz ◽  
Baxter Abraham ◽  
Elisa Biasin ◽  
Tim Brandt van Driel ◽  
Alessandro Gallo ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Complex Reaction ◽  
Reaction Intermediates ◽  
Intermediate States

Femtosecond EXAFS is implemented at an XFEL and can be used to observe short-lived intermediate states of photoexcited transition metal complexes in solution.

Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel–Crafts hydroxyalkylation of indoles

2014 ◽  
Vol 43 (29) ◽  
pp. 11260-11268 ◽  
Author(s):  
Daniel Carmona ◽  
M. Pilar Lamata ◽  
Antonio Sánchez ◽  
Fernando Viguri ◽  
Ricardo Rodríguez ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Transition Metal Complex ◽  
Acid Catalysts ◽  
Bronsted Acid ◽  
Chiral Transition ◽  
Brönsted Acid ◽  
Bronsted Acid Catalysts

Water is the catalyst! The transition metal complex “only” modulates its acidity and provides a chiral environment.

scholarly journals Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics

2020 ◽  
Vol 22 (34) ◽  
pp. 19326-19341
Author(s):  
Aditya Nandy ◽  
Daniel B. K. Chu ◽  
Daniel R. Harper ◽  
Chenru Duan ◽  
Naveen Arunachalam ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Spin State ◽  
Large Scale ◽  
Transition Metal Complex ◽  
Large Data ◽  
Data Set ◽  
Large Data Set

The origin of distinct 3d vs. 4d transition metal complex sensitivity to exchange is explored over a large data set.

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’.

Metal complex interactions with DNA

2015 ◽  
Vol 44 (8) ◽  
pp. 3505-3526 ◽  
Author(s):  
Benjamin J. Pages ◽  
Dale L. Ang ◽  
Elisé P. Wright ◽  
Janice R. Aldrich-Wright
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Spectroscopic Techniques ◽  
Binding Modes ◽  
Dna Interactions ◽  
Diverse Range ◽  
Dna Structures ◽  
Complex Interactions

Increasing numbers of DNA structures are being revealed using a diverse range of transition metal complexes and biophysical spectroscopic techniques. Here we present a review of metal complex-DNA interactions in which several binding modes and DNA structural forms are explored.

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