Special Issue "Carbon Ligands: From Fundamental Aspects to Applications"
Deadline for manuscript submissions: 31 July 2020.
Interests: My research activities focus on main group chemistry, coordination chemistry, and homogeneous catalysis. Special attention is given on the design, the coordination, and the catalytic properties of electron-rich neutral carbon ligands (carbenes, phosphonium ylides) and electron-poor cationic phosphorus ligands (cyclopropenio- and imidazoliophosphines)
Homogeneous catalysis owes its tremendous development to the advent of a wide range of ligands with well-defined electronic and steric properties, which can finely control the reactivity of organometallic complexes. The ligands involved in catalysis have been centered for a long time on elements of group 15, and it is only more recently that carbon representatives have proved to be valuable alternatives with the emergence of the famous cyclic diaminocarbenes (NHCs). Beyond their activity, the predominance of N- and P-based ligands can be explained by their high stability as opposed to the carbon ligands that have long been thought to be unstable. The isolation of the first stable carbenes proved to be a trigger in the minds of chemists, leading in a short time to remarkable advances in the field of homogeneous catalysis. From there, considerable efforts have been undertaken and carbene ligands have become unavoidable surpassing even their illustrious predecessors in some transformations. Like carbenic species (NHCs, aNHCs (MICS), CAACs, BACs, non-NHCs, etc.), onium (P+, N+, S+) ylides and related (bis-ylides, carbones, carbodiphosphoranes, carbodicarbenes, NHOs, etc.) which are charge-neutral in their free state and act as strong σ-donor ligands, have experienced a revival of interest, thus, confirming their potential as Lewis bases in main group chemistry, coordination chemistry, and in homogeneous catalysis.
The aim of this Special Issue is to provide a contemporary overview of the advances in carbon ligand chemistry. From fundamental aspects to applications, all contributions involving carbon ligands, where the coordinating carbon atom is either of C-sp2 type as in carbenic derivatives, or of C-sp3 type as in ylidic species, are thus welcome.
Dr. Yves Canac
Manuscript Submission Information
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- Carbon ligand
- Carbon–metal bond
- Coordination mode
- Organometallic complex
- Main group chemistry
- Coordination chemistry
- Homogeneous catalysis
The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.
Title: Hybrid Gold(I) NHC-Artemether Complexes to Target Falciparum Malaria Parasites
Manel Oujia,b,$, Guillaume Barnouina,$, Álvaro Fernández Álvareza, Jean-Michel Augereaua,b, Catherine Hemmerta,*, Françoise Benoit-Vicala,b,c,* and Heinz Gornitzkaa,*
a CNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France
b Institut de Pharmacologie et de Biologie Structurale, IPBS, Université de Toulouse, CNRS, UPS, France
c INSERM, Institut National de la Santé et de la Recherche Médicale, France
$ Participated equally to this work.
Title: Photoluminescent Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands
Authors: Marius Klein; Nemrud Demirela; Alexander Schinabeckb; Hartmut Yersin; Jörg Sundermeyer
Affiliation: 1. Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany 2. Institute for Physical Chemistry, University of Regensburg, 93040 Regensburg, Germany
Abstract: A series of dinuclear copper(I) complexes of multifunctional N,C,N- and P,C,P- carbodiphosphorane (CDP) ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated, spectroscopically and structurally characterized. Their common structural motive is the central double ylidic carbon atom acting as 4-electron donor bridging two copper(I) atoms in close proximity. Neutral complexes were obtained via reaction with CuCl, CuI, and CuSPh precursors, respectively, or via reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalent of [Cu(NCMe)4]PF6, followed by the addition of either two equivalents of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of a bridging bisphosphine ligand (DPEPhos, XantPhos, dppf). Carbodiphosphorane (CDP(CH2PPh2)2 (13) was isolated upon treating [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. However, NMR spectroscopy and DFT calculations reveal, that the double ylidic CDP form of 13 is not the most stable tautomer in gas phase and solution. Nevertheless, the CDP form is trapped from its tautomeric equilibrium, if CuCl, CuI, and CuSPh are reacted with 13 and dinuclear CDP complexes 14-16 are formed. In sharp contrast, 12, the protonated form of neutral zwitterionic ligand 13, acts as cationic pincer ligand towards CuX Lewis acids. Most of the complexes show photoluminescence (PL) upon UV excitation at ambient temperature. For example, for [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and [(CuSPh)2(CDP(CH2PPh2)2] (16), PL quantum yields (PL) were determined to 36%, and 60%, respectively.