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Inorganics
Special Issues
Metal Mediated Small Molecule Activation
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Metal Mediated Small Molecule Activation

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 May 2018) | Viewed by 13063

Special Issue Editor

Prof. Dr. Marc D. Walter

E-Mail Website
Guest Editor
Technische Universitat Braunschweig, Institute for Inorganic and Analytic Chemistry, Braunschweig, Germany
Interests: small molecule activation; d- and f-block metals; reactive metal complexes

Special Issue Information

Dear Colleagues,

Small molecules, such as N2, O2, H2, CO2 and CH4, are of biological or industrial relevance and originate from metabolic cycles or industrial processes, which make them inexpensive and readily accessible. However, because of their thermodynamic stability, selective activation and functionalization to value-added products or chemical fuels is not a trivial task and present a significant challenge to the chemical community. In this field, molecular chemists are ideally positioned to contribute to this rapidly expanding area, e.g., by creative ligand design, synthesis, detailed mechanistic and spectroscopic studies. Furthermore, in recent years, catalysts based on non-precious and environmentally benign metals have been introduced and start challenging the traditional ones based on precious metals. This Special Issue intends to cover these developments by providing a platform for organometallic and coordination chemists to present their findings covering complex synthesis, spectroscopic studies to stoichiometric or catalytic activation of small molecules.  

Prof. Dr. Marc D. Walter
Guest Editor

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • complex synthesis and spectroscopy
  • mechanistic studies
  • non-precious metals
  • ligand design
  • small molecule activation

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Published Papers (3 papers)

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Research

22 pages, 6211 KiB  
Article
Fluorescent Bis(guanidine) Copper Complexes as Precursors for Hydroxylation Catalysis
by Florian Strassl, Alexander Hoffmann, Benjamin Grimm-Lebsanft, Dieter Rukser, Florian Biebl, Mai Anh Tran, Fabian Metz, Michael Rübhausen and Sonja Herres-Pawlis
Inorganics 2018, 6(4), 114; https://doi.org/10.3390/inorganics6040114 - 20 Oct 2018
Cited by 7 | Viewed by 4795
Abstract
Bis(guanidine) copper complexes are known for their ability to activate dioxygen. Unfortunately, until now, no bis(guanidine) copper-dioxygen adduct has been able to transfer oxygen to substrates. Using an aromatic backbone, fluorescence properties can be added to the copper(I) complex which renders them useful [...] Read more.
Bis(guanidine) copper complexes are known for their ability to activate dioxygen. Unfortunately, until now, no bis(guanidine) copper-dioxygen adduct has been able to transfer oxygen to substrates. Using an aromatic backbone, fluorescence properties can be added to the copper(I) complex which renders them useful for later reaction monitoring. The novel bis(guanidine) ligand DMEG2tol stabilizes copper(I) and copper(II) complexes (characterized by single crystal X-ray diffraction, IR spectroscopy, and mass spectrometry) and, after oxygen activation, bis(µ-oxido) dicopper(III) complexes which have been characterized by low-temperature UV/Vis and Raman spectroscopy. These bis(guanidine) stabilized bis(µ-oxido) complexes are able to mediate tyrosinase-like hydroxylation activity as first examples of bis(guanidine) stabilized complexes. The experimental study is accompanied by density functional theory calculations which highlight the special role of the different guanidine donors. Full article
(This article belongs to the Special Issue Metal Mediated Small Molecule Activation)
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7 pages, 1256 KiB  
Communication
Non-Selective Dimerization of Vinyl Silanes by the Putative (Phenanthroline)PdMe Cation to 1,4-Bis(trialkoxysilyl)butenes
by Sandun Perera and Michael Findlater
Inorganics 2018, 6(4), 102; https://doi.org/10.3390/inorganics6040102 - 25 Sep 2018
Viewed by 3374
Abstract
Activation of the dialkylpalladium complex (phen)Pd(CH3)2 (phen = 1,10-phenanthroline) with B(C6F5)3 affords a competent catalyst for the dimerization of vinyl silanes. All organic products of the catalytic dimerization of trialkoxyvinylsilanes were characterized by in situ [...] Read more.
Activation of the dialkylpalladium complex (phen)Pd(CH3)2 (phen = 1,10-phenanthroline) with B(C6F5)3 affords a competent catalyst for the dimerization of vinyl silanes. All organic products of the catalytic dimerization of trialkoxyvinylsilanes were characterized by in situ NMR spectroscopy and GC–MS. The putative palladium cation was characterized by NMR spectroscopy. Upon activation, the palladium complex generated products in moderate yield (60–70%) and selectivity (~60:40, dimer:disproportionation products). Full article
(This article belongs to the Special Issue Metal Mediated Small Molecule Activation)
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9 pages, 1353 KiB  
Article
Phenylacetylene and Carbon Dioxide Activation by an Organometallic Samarium Complex
by Violaine Goudy, Mathieu Xémard, Simon Karleskind, Marie Cordier, Carlos Alvarez Lamsfus, Laurent Maron and Grégory Nocton
Inorganics 2018, 6(3), 82; https://doi.org/10.3390/inorganics6030082 - 21 Aug 2018
Cited by 7 | Viewed by 4276
Abstract
Small molecule activation is a topic of growing importance and the use of low-valent f-elements to perform these reactions is nowadays well established. The complex Cptt2Sm(thf) (1, Cptt = 1,3-(tBu)2Cp) is shown to [...] Read more.
Small molecule activation is a topic of growing importance and the use of low-valent f-elements to perform these reactions is nowadays well established. The complex Cptt2Sm(thf) (1, Cptt = 1,3-(tBu)2Cp) is shown to activate the alkyne C–H bond of phenylacetylene to form the Cptt2Sm(C≡C–Ph)(thf) complex. The subsequent reaction of this Sm(III) complex with CO2 leads to the CO2 insertion, yielding a dimeric [Cptt2Sm(O2C–C≡C–Ph)]2 complex (2), in which the carbon dioxide has been inserted in the Sm–C bond. Along with the experimental chemical structure analysis, theoretical calculations have been performed in order to rationalize the formation of 1 and 2. Full article
(This article belongs to the Special Issue Metal Mediated Small Molecule Activation)
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