Cover Picture

Free Access

Front Cover: The TpxM Core in Csp3–H Bond Functionalization Reactions: Comparing Carbene, Nitrene, and Oxo Insertion Processes (Tpx = Scorpionate Ligand; M = Cu, Ag) (Eur. J. Inorg. Chem. 11-12/2020)

  • Pages: 868
  • First Published: 12 March 2020
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The Front Cover shows the three reactive metal intermediates bearing carbene, nitrene, or oxo groups, which lead to the carbon-hydrogen bond, integrated into a background picture inspired by the westbound trip of Columbus in 1492 with three ships, Pinta, Niña, and flagship Santa Maria. The trip started from Palos de la Frontera, which is close to Huelva, where the authors work. Credit Benoit Chartron and Marian Mocanu (Depositphotos.com). Thanks to Dr. Ivan Rivilla, who adapted the graphics for this cover design. More information can be found in the Minireview by M. M. Díaz-Requejo and P. J. Pérez. For more on the story behind the cover research, see the Cover Profile.

Cover Profile

The TpxM Core in Csp3–H Bond Functionalization Reactions: Comparing Carbene, Nitrene, and Oxo Insertion Processes (Tpx = Scorpionate Ligand; M = Cu, Ag)

  • Pages: 869
  • First Published: 12 March 2020
Description unavailable

Alkanes usually display several different reaction sites: primary, secondary, and tertiary carbon–hydrogen bonds. The control of the selectivity toward each site is difficult, a challenge that is currently pursued by the scientists working in this area …

Read more about the story behind the cover in the Cover Profile and about the research itself in the Minireview by M. M. Díaz-Requejo and P. J. Pérez.

Cover Picture

Free Access

Cover Feature: Conjugate Addition Routes to 2-Alkyl-2,3-dihydroquinolin-4(1H)-ones and 2-Alkyl-4-hydroxy-1,2-dihydroquinoline-3-carboxylates (Eur. J. Inorg. Chem. 11-12/2020)

  • Pages: 870
  • First Published: 12 March 2020
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The Cover Feature shows new chiral tetrahydroquinoline carboxylates attained by asymmetric copper-catalyzed 1,4-addition of AlR3 “floating” above the countryside of Camerino, where the 12th International School of Organometallic Chemistry was held. More information can be found in the Full Paper by S. Woodward et al.

Free Access

Cover Feature: In water Markovnikov hydration and one-pot reductive hydroamination of terminal alkynes under Ruthenium nanoparticle catalysis (Eur. J. Inorg. Chem. 11-12/2020)

  • Pages: 871
  • First Published: 12 March 2020
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The Cover Feature shows a procedure that enables the reductive hydro-amination of aromatic alkynes in water as the only solvent. The reagents and the Ru catalyst are assembled within nanomicelles that release the final product into the water. The product is recovered from the water surface. The background shoreline image reminds us of the eternal relationship between the sea and mankind, who stays on dry land and obtains resources out of the sea. Nanomicellar reactors do the same, generating products in water and releasing them out of the water after the man on the beach has had fun playing with nanomicellar chemistry. More information can be found in the Communication by M. Taddei et al.

Guest Editorial

12th ISOC

Free Access

“ISOC”, International School of Organometallic Chemistry: A Success Story

  • Pages: 872-874
  • First Published: 23 March 2020
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Guest Editor Claudio Pettinari describes the organization of the first School of Organometallic Chemistry, telling the story of its development to become the highly successful International School anticipating its 13th edition in 2021. He then introduces the 24 contributions in this double Special Issue of EurJIC in celebration of the 12th edition.

Essay

Organometallic Redox Reactions

Sites of Electron Transfer Reactivity in Organometallic Compounds

  • Pages: 875-878
  • First Published: 13 March 2020
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Three fundamentally different locations can be identified for electron transfer in organometallic compounds, potentially leading to different kinds of redox reactivity and physical properties. The metal, the C-bonded organic ligand, and/or the supporting ancillary ligands may be involved, either separately or in mixed, electron delocalized form.

Minireviews

Alkane Functionalization | Very Important Paper

The TpxM Core in Csp3–H Bond Functionalization Reactions: Comparing Carbene, Nitrene, and Oxo Insertion Processes (Tpx = Scorpionate Ligand; M = Cu, Ag)

  • Pages: 879-885
  • First Published: 09 December 2019
Description unavailable

A comparison of three reactions involving alkane C–H functionalization by carbene, nitrene, and oxo insertion using trispyrazolylborate complexes of copper or silver is presented. The effect of the ligand scaffold, both steric and electronic, in the reaction outcome is discussed toward a global overview for future catalyst design.

Minireview

Haloalkynes | Very Important Paper

Metal-Catalyzed Hydrofunctionalization Reactions of Haloalkynes

  • Pages: 886-898
  • First Published: 13 October 2019
Description unavailable

Metal-catalyzed hydrofunctionalization reactions of haloalkynes (chloro-, bromo- and iodoalkynes) are reviewed, covering examples of the selective addition of C–H, O–H, N–H, S–H and X–H (X = halide) bonds.

Artificial Photosynthesis | Very Important Paper

Dye-Sensitized Heterogeneous Photocatalysts for Green Redox Reactions

  • Pages: 899-917
  • First Published: 29 November 2019
Description unavailable

Dye-sensitized photocatalysts (DSP) are currently among the most promising systems employed for the production of solar fuels. In this review, selected examples of the use of DSP for H+ and/or CO2 reduction are discussed, highlighting how materials properties and catalyst composition can affect the efficiency of such “artificial photosynthetic” processes.

Minireviews

Anticancer Agents

Five-Coordinate Platinum(II) Compounds as Potential Anticancer Agents

  • Pages: 918-929
  • First Published: 11 September 2019
Description unavailable

The review traces the progress of the investigation on the anticancer activity of five-coordinate Pt(II) complexes, and the subsequent refinements in the structures. It also reports their synthesis, general properties, cytotoxic activity and ability to interact with biological macromolecules.

Triphenyltin(IV) Carboxylates

Biological Evaluation of Azo- and Imino-Based Carboxylate Triphenyltin(IV) Compounds

  • Pages: 930-941
  • First Published: 19 January 2020
Description unavailable

The review highlights the syntheses, structures, and biological properties of organotin(IV) benzoates containing –N=N– (azo group) or –C=N– (imine group) appended skeletons.

Palladium Catalysts

Catalytic Domino Annulations through η3-Allylpalladium Chemistry: A Never-Ending Story

  • Pages: 942-961
  • First Published: 09 December 2019
Description unavailable

Annulative η3-allylpalladium chemistry has been a trending topic in catalysis since the 80's and is still a challenging area of research through the discovery of new reactivities, the development of enantioselective versions and their applications in total synthesis. The latest developments in this field are summarized here.

Gold Catalysts

Vinyl-/Furoindoles and Gold Catalysis: New Achievements and Future Perspectives for the Synthesis of Complex Indole Derivatives

  • Pages: 962-977
  • First Published: 15 November 2019
Description unavailable

The use of substituted or polycyclic indoles in reactions with gold-activated π-systems allows for the synthesis of new classes of carbazole derivatives and highly functionalized indoles under mild conditions and with high level of regio diastereo and enantio selectivities.

Water Splitting

Molecular Organic Sensitizers for Photoelectrochemical Water Splitting

  • Pages: 978-999
  • First Published: 26 February 2020
Description unavailable

Molecular photosensitizers are gaining increasing importance in sunlight-induced artificial synthesis processes, such as water splitting, by the photoelectrochemical approach. In recent years, metal-free organic dyes have emerged as a new frontier for the evolution of the sector thanks to their wide structural variety and key properties, for a more efficient solar generation of clean fuels.

Communications

Alkyne Hydroamination | Very Important Paper

In Water Markovnikov Hydration and One-Pot Reductive Hydroamination of Terminal Alkynes under Ruthenium Nanoparticle Catalysis

  • Pages: 1000-1003
  • First Published: 12 December 2019
Description unavailable

The first example of one-pot single-step reductive amination of terminal acetylenes in the presence of Ru nanoparticle-nanomicelle catalyst in water is described. The intermediate hydration product can be also isolated.

Rhenium NHCs

Expanding the Scope of Water-Stable Rhenium(V)-NHC Complexes – Synthesis, Characterization, and Derivatization

  • Pages: 1004-1010
  • First Published: 14 November 2019
Description unavailable

The synthesis of novel ReV complexes bearing a tridentate NHC scorpionate ligand is reported. The complexes were fully characterized, including X-ray structural analyses. Additionally, their stability towards air and moisture was investigated. The new ReV NHC scorpionate motif discussed herein is one step further in the direction towards water-stable Re-based metallodrugs.

Full Papers

Copper-Catalyzed 1,4-Addition | Very Important Paper

Conjugate Addition Routes to 2-Alkyl-2,3-dihydroquinolin-4(1H)-ones and 2-Alkyl-4-hydroxy-1,2-dihydroquinoline-3-carboxylates

  • Pages: 1011-1017
  • First Published: 29 November 2019
Description unavailable

Directing ester functions (R = CO2Et) “give a big hand” to copper catalysed 1,4-additions of organometallics to medicinally relevant quinolin-4(1H)-ones. In the absence of any directing group only 11 % ee is realised for the addition of EtMgBr. In the presence of the CO2Et activating group, AlEt3 may be added in up to 82 % ee providing 6-halo building block starting materials for quinolone species.

Organometallic Pt Compounds

One-Pot Synthesis of New Organometallic Compounds with Platinum-Carbon Bond

  • Pages: 1018-1026
  • First Published: 06 December 2019
Description unavailable

σ-Bonded organometallic platinum compounds containing ortho-metalated para-nitro-benzamidate or 1-naphthalene-methylamine with potential antitumor activity have been prepared by one-pot synthesis. An intermediate dimeric species with a benzamidate ligand bridging two Pt units has been isolated, and it appeared to be a mixture of a head-to-head (HH) and a head-to-tail (HT) isomers.

Anticancer Zn Complexes

Zinc(II) Complexes of Acylpyrazolones Decorated with a Cyclohexyl Group Display Antiproliferative Activity Against Human Breast Cancer Cells

  • Pages: 1027-1039
  • First Published: 11 September 2019
Description unavailable

Zinc(II) acylpyrazolone complexes were synthesized, decorated with a long aliphatic chain or a cyclohexyl group in the acyl moiety of the ligands, the latter displaying antiproliferative activity against MCF-7 human breast cancer cell line, additionally improved when an ancillary bipyridine is present in the zinc coordination environment.

Anticancer Organogold Complexes

Open Access

Exploring the Reactivity and Biological Effects of Heteroleptic N-Heterocyclic Carbene Gold(I)-Alkynyl Complexes

  • Pages: 1040-1051
  • First Published: 03 January 2020
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Two families of heteroleptic N-heterocyclic carbene gold(I)-alkynyl complexes have been synthesized and characterized by different methods. Their reactivity with model thiols has been studied by NMR spectroscopy and DFT calculations. Moreover, preliminary studies on the compounds' reactivity with DNA and antiproliferative effects have been conducted.

Anticancer Complexes | Very Important Paper

Open Access

Ligand-Controlled Reactivity and Cytotoxicity of Cyclometalated Rhodium(III) Complexes

  • Pages: 1052-1060
  • First Published: 20 November 2019
Description unavailable

The chemical reactivity and cytotoxicity of half-sandwich organo-rhodium complexes can be controlled by the monodentate ligand. Chlorido complexes show faster hydrolysis and higher catalytic efficiency, but pyridine complexes exhibit higher cytotoxicity with lower cellular Rh accumulation. The pyridine complexes act as ROS scavengers, while the chlorido analogues elevate ROS levels in cancer cells.

Ruthenium-Biotin Conjugates

Conjugating Biotin to Ruthenium(II) Arene Units via Phosphine Ligand Functionalization

  • Pages: 1061-1072
  • First Published: 29 October 2019
Description unavailable

Robust ruthenium(II) arene compounds incorporating biotin through a phosphine linkage were synthesized and assessed for their cytotoxicity against several cancer cell lines with different levels of biotin transporter expression, and for their apparent affinity to avidin.

Ditopic NHC Ligands

Silver(I) and Nickel(II) Complexes with Oxygen- or Nitrogen-Functionalized NHC Ditopic Ligands and Catalytic Ethylene Oligomerization

  • Pages: 1073-1087
  • First Published: 24 November 2019
Description unavailable

With potentially bi- or tri-dentate hybrid NHC ligands, the donor function Y coordinates to the metal under conditions that can be analyzed by modular ligand design and chemical modifications of the donor groups (here ether or amine). Anionic [NiBr3(NHC)] undergoes H-bonding with its imidazolium cation.

Polymerization Cocatalysts | Very Important Paper

On the Nature of the Lewis Acidic Sites in “TMA-Free” Phenol-Modified Methylaluminoxane

  • Pages: 1088-1095
  • First Published: 21 October 2019
Description unavailable

Reaction of BHT-modified MAO with the N-donors pyridine and bipyridine leads to neutral AlMe2(bht)(py) and cationic [AlMe(bht)(bipy)]+, respectively. It appears that “structural” AlMe3, needed to stabilize the Al-clusters of MAO and generate Lewis acidic [AlMe2]+ for precatalyst activation, is transformed into analogous “structural” AlMe2(bht) in MAO/BHT, capable of releasing [AlMe(bht)]+.

FLP Cycloaddition | Very Important Paper

Borane-Mediated Vinylphosphane Cycloaddition to Conjugated Ynones

  • Pages: 1096-1100
  • First Published: 12 November 2019
Description unavailable

Dimesitylvinylphosphane undergoes a stepwise [3+2] type cycloaddition reaction with conjugated ynones to give the five-membered phosphorus heterocyclic products.

Disproportionation Reactions

Base-Initiated Formation of FeI–PNP Pincer Complexes

  • Pages: 1101-1105
  • First Published: 08 October 2019
Description unavailable

Fe(I) PNP pincer complexes of the type [Fe(PNPNH)(CO)2]+ were prepared from Fe(II) complexes of the type [Fe(PNPNH)(CO)(Cl)2] and KOtBu in an aprotic solvent. In these reactions, the formation of free PNP ligand together with unknown Fe(III) species is observed due to a disproportionation process of the type 2FeII → FeI and FeIII.

In/Zn Reduction Catalysts

On the Virtue of Indium in Reduction Reactions. A Comparison of Reductions Mediated by Indium and Zinc: Is Indium Metal an Effective Catalyst for Zinc Induced Reductions?

  • Pages: 1106-1113
  • First Published: 08 November 2019
Description unavailable

The merit of indium over zinc in reductions has been investigated. The reduction of N,N-disubstituted hydroxylamines to the corresponding amines was the only transformation for which use of indium is advantageous and a catalytic indium procedure was equally efficient.

Green Ru Catalysts

Imidazolium Salts of Ruthenium Anionic Cyclopentadienone Complexes: Ion Pair for Bifunctional Catalysis in Ionic Liquids

  • Pages: 1114-1122
  • First Published: 18 October 2019
Description unavailable

Bis(carbonyl) cyclopentadienone ruthenium complexes ion paired with variously functionalized imidazolium salts are suitable as bifunctional catalysts for transfer hydrogenation on a model compound, such as 4-fluoroacetophenone, in ionic liquid media. The biphasic system allows recovery and recycling of the catalyst.

Dual Catalysis

Phenoxylation of Alkynes through Mono- and Dual Activation Using Group 11 (Cu, Ag, Au) Catalysts

  • Pages: 1123-1134
  • First Published: 06 January 2020
Description unavailable

The complexity of the C–O bond formation when alkynes are mixed with alcohols in a system catalysed by one or two metal moieties is unveiled by energy decomposition analyses.