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Inorganics
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Feature Papers in Organometallic Chemistry 2024
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Feature Papers in Organometallic Chemistry 2024

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

Deadline for manuscript submissions: closed (31 December 2024) | Viewed by 24618

Special Issue Editors

Prof. Dr. Axel Klein

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Faculty of Mathematics and Natural Sciences, Department of Chemistry, Institute for Inorganic Chemistry, University of Cologne, Greinstraße 6, 50939 Köln, Germany
Interests: coordination chemistry; organometallics; catalysis; transition metals; photophysics; electrochemistry
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Francis Verpoort

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Guest Editor
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430000, China
Interests: organometallics; metal-organic frameworks; porous organic polymers; electrocatalysis; photocatalysis; thermocatalysis; reaction mechanisms; metal-organic framework derivatives; clean energy technologies; environmental applications; water splitting; fuel cells; organic catalysis; CO2 capture
Special Issues, Collections and Topics in MDPI journals
Dr. Shuang Xiao

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Guest Editor
Shenzhen Key Laboratory of Ultraintense Laser and Advanced Material Technology, Center for Intense Laser Application Technology (iLaT) and College of Engineering Physics, Shenzhen Technology University, Shenzhen 518118, China
Interests: organometal halide perovskite; photovoltaics; radiation detection
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Our Special Issue "10th Anniversary of Inorganics: Organometallic Chemistry" in 2023 has been a great success (you can reference this SI here). As we feel that there is far more potential in this topic, and we have received some further agreements for manuscript submissions, we want to launch the Special Issue "Feature Papers in Organometallic Chemistry 2024" as a follow-up SI project. We invite all colleagues working in the field of organometallic chemistry to submit a contribution within this SI to shed light on this important aspect of chemistry.

Communications, full research papers, and reviews describing the synthesis of organometallic compounds, their use or relevance in catalysis, and their application in important fields such as luminescent materials, photochemical energy conversion, and bio-medical applications in diagnosis and treatment, just to name a few, are welcome.

Prof. Dr. Axel Klein
Prof. Dr. Francis Verpoort
Dr. Shuang Xiao
Guest Editors

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Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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 2200 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

  • organometallic compounds
  • transition metals
  • lanthanides
  • actinides
  • main group elements
  • organometallic compounds in catalysis
  • organometallic compounds as molecular emitters
  • organometallic compounds in bio-imaging
  • organometallic compounds in electroluminescence
  • organometallic compounds in sensing
  • organometallic compounds in energy conversion
  • organometallic compounds in light harvesting
  • organometallic compounds in magnetism
  • organometallic compounds in photonics
  • organometallic compounds in coordination polymer
  • organometallic compounds in metal–organic framework
  • organometallic compounds in materials science
  • organometallic compounds in supramolecular chemistry and in crystal engineering
  • computational/theoretical organometallic chemistry
  • further areas for development and new perspectives

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Published Papers (9 papers)

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Research

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18 pages, 3247 KiB  
Article
Pyridine vs. Thiazole in Cyclometalated N^C^N Ni(II) Complexes
by Lukas Kletsch, Rose Jordan, Julian Strippel, David A. Vicic and Axel Klein
Inorganics 2025, 13(2), 41; https://doi.org/10.3390/inorganics13020041 - 1 Feb 2025
Viewed by 697
Abstract
Six N^C^N cyclometalated Ni(II) complexes [Ni(N^C^N)Cl] or [Ni(N^C^N’)Br] with symmetric N^C^N or non-symmetric N^C^N’ ligands in which the peripheral N-groups were varied with pyridine (Py), 4-thiazole (4Tz), 2-thiazole (2Tz), and 2-benzothiazole (2Btz) complementing the previously reported complexes with di(2-pyridyl)phenide ligands [Ni(Py(Ph)Py)X] X = [...] Read more.
Six N^C^N cyclometalated Ni(II) complexes [Ni(N^C^N)Cl] or [Ni(N^C^N’)Br] with symmetric N^C^N or non-symmetric N^C^N’ ligands in which the peripheral N-groups were varied with pyridine (Py), 4-thiazole (4Tz), 2-thiazole (2Tz), and 2-benzothiazole (2Btz) complementing the previously reported complexes with di(2-pyridyl)phenide ligands [Ni(Py(Ph)Py)X] X = Cl or Br. The non-symmetric [Ni(N^C^N’)Br] complexes were synthesized from NiBr2 and N^CH^N’ protoligands through base-assisted nickelation, while the symmetric [Ni(N^C^N)Cl] complexes were received from the N^C(Cl)^N protoligands and [Ni(COD)2] (COD = 1,5-cyclooctadiene). Introduction of 4Tz on both sides shifted the electrochemical gap ΔEexp = Eox–Ered and the long wavelength UV-vis absorption maxima of the complexes to higher energies, while 2Tz leads to a shift to lower energies. When introducing only one 4Tz or 2Tz as peripheral groups, the remaining PhPy moiety dominates the electronic properties and electrochemistry and photophysics are very similar to the Py(Ph)Py derivatives. In contrast to this, introduction of 2Btz shifts both values to lower energies, regardless of one or two 2Btz groups and the 2Btz moiety dominates the character of the frontier molecular orbitals of the complexes, as DFT calculations show. Long-wavelength UV-vis absorptions vary from 416 to 443 nm, and their energies correlate well with the first reduction potentials. Negishi-type C–C cross-coupling reactions gave total yields ranging from 1 to 60% and cross-coupling yields from 1 to 44%. The reactivities correlate roughly with the first reduction potentials. Facilitated reduction (E around –2 or higher) goes generally along with improved performance, making the thiazole-containing complexes interesting candidates for such catalysis. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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15 pages, 2918 KiB  
Communication
Monodentate Ligands in X-Cu(I)-Y Complexes—Structural Aspects
by Milan Melník, Veronika Mikušová and Peter Mikuš
Inorganics 2024, 12(11), 279; https://doi.org/10.3390/inorganics12110279 - 30 Oct 2024
Cited by 1 | Viewed by 1222
Abstract
This structural study examines over 102 coordinate Cu(I) complexes with compositions such as C-Cu-Y (Y=HL, OL, NL, SL, SiL, BL, PL, Cl, Br, I, AlL, or SnL), N-Cu-Y (Y=OL, Cl), S-Cu-Y (Y=Cl, Br, I), P-Cu-Y (Y=Cl, I), and Se-Cu-Y (Y=Br, I). These complexes [...] Read more.
This structural study examines over 102 coordinate Cu(I) complexes with compositions such as C-Cu-Y (Y=HL, OL, NL, SL, SiL, BL, PL, Cl, Br, I, AlL, or SnL), N-Cu-Y (Y=OL, Cl), S-Cu-Y (Y=Cl, Br, I), P-Cu-Y (Y=Cl, I), and Se-Cu-Y (Y=Br, I). These complexes crystallize into three different crystal classes: monoclinic (seventy-two instances), triclinic (twenty-eight instances), and orthorhombic (eight instances). The Cu-L bond length increases with the covalent radius of the ligating atom. There are two possible geometries for coordination number two: linear and bent. A total of 21 varieties of inner coordination spheres exist, categorized into two hetero-types (C-Cu-Y, i.e., organometallic compounds and X-Cu-Y, i.e., coordination compounds). The structural parameters of hetero Cu(I) complexes were compared with trans-X-Cu (I)-X (homo) complexes and analyzed. The maximum deviations from linearity (180.0°) are, on average, 10.3° for Br-Cu(I)-Br, 16.6° for C-Cu(I)-Sn, and 35.5° for P-Cu(I)-I. These results indicate that ligand properties influence deviation from linearity, increasing in the order of hard < borderline < soft. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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13 pages, 2654 KiB  
Article
Electrochemically Active Copper Complexes with Pyridine-Alkoxide Ligands
by Christopher K. Webber, Erica K. Richardson, Diane A. Dickie and T. Brent Gunnoe
Inorganics 2024, 12(8), 200; https://doi.org/10.3390/inorganics12080200 - 24 Jul 2024
Viewed by 1078
Abstract
Pyridine-alkoxide (pyalk) ligands that support transition metals have been studied for their use in electrocatalytic applications. Herein, we used the pyalk proligands diphenyl(pyridin-2-yl)methanol ([H]PhPyalk, L1), 1-(pyren-1-yl)-1-(pyridin-2-yl)ethan-1-ol ([H]PyrPyalk, L2), 1-(pyridine-2-yl)-1-(thiophen-2-yl)ethan-1-ol ([H]ThioPyalk, L3), and 1-(ferrocenyl)-1-(pyridin-2-yl)ethan-1-ol ([H] [...] Read more.
Pyridine-alkoxide (pyalk) ligands that support transition metals have been studied for their use in electrocatalytic applications. Herein, we used the pyalk proligands diphenyl(pyridin-2-yl)methanol ([H]PhPyalk, L1), 1-(pyren-1-yl)-1-(pyridin-2-yl)ethan-1-ol ([H]PyrPyalk, L2), 1-(pyridine-2-yl)-1-(thiophen-2-yl)ethan-1-ol ([H]ThioPyalk, L3), and 1-(ferrocenyl)-1-(pyridin-2-yl)ethan-1-ol ([H]FePyalk, L4) to synthesize CuII complexes that vary in nuclearity and secondary coordination sphere. Also, the proligand 1-(ferrocenyl)-1-(5-methoxy-pyridin-2-yl)ethan-1-ol ([H]FeOMePyalk, L5) was synthesized with a methoxy substituted pyridine; however, the isolation of a CuII complex ligated by L5 was not possible. Under variable reaction conditions, the pyalk ligands reacted with CuII precursors and formed either mononuclear or dinuclear CuII complexes depending on the amount of ligand added. The resulting complexes were characterized by single crystal X-ray diffraction, elemental analysis, and cyclic voltammetry. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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15 pages, 4407 KiB  
Article
Palladium-Catalyzed Cross-Coupling Reaction via C–H Activation of Furanyl and Thiofuranyl Substrates
by Neslihan Şahin, İsmail Özdemir and David Sémeril
Inorganics 2024, 12(6), 175; https://doi.org/10.3390/inorganics12060175 - 20 Jun 2024
Viewed by 1374
Abstract
The present study explores the potential of four NHC-palladium(II) complexes derived from (Z)- or (E)-styryl-N-alkylbenzimidazolium salts, namely trans-dichloro-[(Z)-1-styryl- 3-benzyl-benzimidazol-2-yliden]pyridine palladium(II) (6), trans-dichloro-[(E)-1-styryl-3-benzyl- benzimidazol-2-yliden]pyridine palladium(II) (7), trans-dichloro-[( [...] Read more.
The present study explores the potential of four NHC-palladium(II) complexes derived from (Z)- or (E)-styryl-N-alkylbenzimidazolium salts, namely trans-dichloro-[(Z)-1-styryl- 3-benzyl-benzimidazol-2-yliden]pyridine palladium(II) (6), trans-dichloro-[(E)-1-styryl-3-benzyl- benzimidazol-2-yliden]pyridine palladium(II) (7), trans-dichloro-[(Z)-1-styryl-3-(3-fluorobenzyl)- benzimidazol-2-yliden]pyridine palladium(II) (8) and trans-dichloro-[(E)-1-styryl-3- (3-fluorobenzyl)-benzimidazol-2-yliden]pyridine palladium(II) (9), to be use as pre-catalysts for the cross-coupling reactions between furanyl or thiofuranyl derivatives and arylbromides via the C–H activation of the heterocycles. The structures of the four Pd(II) complexes have been elucidated through the use of multinuclear NMR, FT-IR and mass spectroscopy. Furthermore, the cis or trans conformation of the styryl substituents and the geometry of two different compounds was substantiated by single-crystal X-ray diffraction, which was carried out on organometallic species 6, 8 and 9. After the optimization of catalytic conditions, which was carried out with 1 mol% of pre-catalyst with KOAc as a base in dimethylacetamide at 120 °C for 3 h, complex 6 proved to be the most effective pre-catalyst agent, with full or quasi full conversions being observed in the cross-coupling of 4-bromoacetophenone with 2-butylfuran, 1-(2-furanyl)-ethanone, furfuryl acetate, furfural, 1-(2-thienyl)-ethanone, thenaldehyde and 2-methylthiophene. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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12 pages, 4063 KiB  
Article
Theoretical Studies on the Insertion Reaction of Polar Olefinic Monomers Mediated by a Scandium Complex
by Xin Wen, Kaipai Ren, Wenzhen Zhang, Guangli Zhou and Yi Luo
Inorganics 2024, 12(6), 172; https://doi.org/10.3390/inorganics12060172 - 19 Jun 2024
Viewed by 979
Abstract
This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory [...] Read more.
This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory (DFT) calculations and multivariate linear regression (MLR) methods. The chain initiation step of the insertion reaction could be described by the poisoning effect and the ease of monomer insertion, which could be represented via the DFT-calculated energy difference between σ- and π-coordination complexes (ΔΔE) and insertion energy barrier (ΔG≠), respectively. The results indicate that ΔΔE and ΔG≠ can be predicted by only several descriptors using multiple linear regression methods, with a root mean squared error (RMSE) of less than 2.5 kcal/mol. Furthermore, the qualitative analysis of the MLR models provided effective information on the key factors governing the insertion reaction chain initiation. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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19 pages, 6540 KiB  
Article
Supramolecular Assemblies in Mn(II) and Zn(II) Metal–Organic Compounds Involving Phenanthroline and Benzoate: Experimental and Theoretical Studies
by Mridul Boro, Subham Banik, Rosa M. Gomila, Antonio Frontera, Miquel Barcelo-Oliver and Manjit K. Bhattacharyya
Inorganics 2024, 12(5), 139; https://doi.org/10.3390/inorganics12050139 - 13 May 2024
Cited by 2 | Viewed by 1924
Abstract
Two new Mn(II) and Zn(II) metal–organic compounds of 1,10-phenanthroline and methyl benzoates viz. [Mn(phen)2Cl2]2-ClBzH (1) and [Zn(4-MeBz)2(2-AmPy)2] (2) (where 4-MeBz = 4-methylbenzoate, 2-AmPy = 2-aminopyridine, phen = 1,10-phenanthroline, 2-ClBzH = [...] Read more.
Two new Mn(II) and Zn(II) metal–organic compounds of 1,10-phenanthroline and methyl benzoates viz. [Mn(phen)2Cl2]2-ClBzH (1) and [Zn(4-MeBz)2(2-AmPy)2] (2) (where 4-MeBz = 4-methylbenzoate, 2-AmPy = 2-aminopyridine, phen = 1,10-phenanthroline, 2-ClBzH = 2-chlorobenzoic acid) were synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction techniques. The crystal structure analysis of the compounds revealed the presence of various non-covalent interactions, which provides stability to the crystal structures. The crystal structure analysis of compound 1 revealed the formation of a supramolecular dimer of 2-ClBzH enclathrate within the hexameric host cavity formed by the neighboring monomeric units. Compound 2 is a mononuclear compound of Zn(II) where flexible binding topologies of 4-CH3Bz are observed with the metal center. Moreover, various non-covalent interactions, such as lp(O)-π, lp(Cl)-π, C–H∙∙∙Cl, π-stacking interactions as well as N–H∙∙∙O, C–H∙∙∙O and C–H∙∙∙π hydrogen bonding interactions, are found to be involved in plateauing the molecular self-association of the compounds. The remarkable enclathration of the H-bonded 2-ClBzH dimer into a supramolecular cavity formed by two [Mn(phen)2Cl2] complexes were further studied theoretically using density functional theory (DFT) calculations, the non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) computational tools. Synergistic effects were also analyzed using molecular electrostatic potential (MEP) surface analysis. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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17 pages, 4125 KiB  
Article
Hypercoordinating Stannanes with C,N-Donor Ligands: A Structural, Computational, and Polymerization Study
by Gloria M. D’Amaral, Desiree N. Bender, Nicola Piccolo, Alan J. Lough, Robert A. Gossage, Daniel A. Foucher and R. Stephen Wylie
Inorganics 2024, 12(4), 122; https://doi.org/10.3390/inorganics12040122 - 18 Apr 2024
Cited by 1 | Viewed by 1737
Abstract
Select triphenyl stannanes bearing either a formally sp2 or sp3 hybridized amine, viz 2-(pyC2H4)SnPh3 (2: py = pyridinyl), 4-(pyC2H4)SnPh3 (3), 2-(pzC2H4)SnPh3 ( [...] Read more.
Select triphenyl stannanes bearing either a formally sp2 or sp3 hybridized amine, viz 2-(pyC2H4)SnPh3 (2: py = pyridinyl), 4-(pyC2H4)SnPh3 (3), 2-(pzC2H4)SnPh3 (4: pz = pyrazyl), and Me2N(CH2)3SnPh3 (6), were prepared and characterized by NMR spectroscopy (119Sn, 13C, 1H), and additionally, in the case of 2, by single crystal X-ray diffraction. Bromination of 2 to yield 2-(pyC2H4)SnPhBr2 (8) was achieved in good yield. X-ray crystallographic analysis of 8 revealed two unique molecules with 5-coordinate Sn centers featuring Sn-N distances of 2.382 (5) and 2.363 (5) Å, respectively. The calculated structures of the non- and hypercoordinating C,N-stannanes (1–9) were in good agreement with available crystallographic data. The relative stabilities of hyper- and non-hypercoordinating conformers obtained from conformational sampling were determined by comparison with reference conformers and by natural bond orbital (NBO) energetic analyses. Reduction of 8 to the dihydride species, 2-(pyC2H4)SnPhH2 (9), and subsequent conversion to the polystannane, -[2-(pyC2H4)SnPh]n- (15), by transition metal-catalyzed dehydropolymerization was also achieved. Evidence for the decomposition of 15 into a redistributed distannoxane, {2-(pyC2H4)SnPh2}2O (16), was also observed. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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14 pages, 4884 KiB  
Article
Design and Construction of a Mixed-Ligand Coordinated Fluorescent Complex and Its Application for Sensing Ions, Antibiotics, and Pesticides in Aqueous Solution
by Gao-Sheng Zhu, Yi Jia, Jia-Yao Ding, Hao Yin, Yan Chen, Bao-Yi Yu, Yan-Ying Zheng and Francis Verpoort
Inorganics 2024, 12(4), 93; https://doi.org/10.3390/inorganics12040093 - 22 Mar 2024
Viewed by 1788
Abstract
In this work, a fluorescent complex [Zn(NTD)2(DTP)2(H2O)2]·(H2O)0.8 (Complex Zn), (H2NTD = 1,4-naphthalenedicarboxylic acid and DTP = 3,5-di(1,2,4-triazol-1-yl)pyridine) was synthesized. The fluorescent complex was characterized by single-crystal X-ray diffraction, [...] Read more.
In this work, a fluorescent complex [Zn(NTD)2(DTP)2(H2O)2]·(H2O)0.8 (Complex Zn), (H2NTD = 1,4-naphthalenedicarboxylic acid and DTP = 3,5-di(1,2,4-triazol-1-yl)pyridine) was synthesized. The fluorescent complex was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric, elemental, infrared spectroscopy, and fluorescence analyses. In the fluorescence sensing tests, Complex Zn exhibited excellent fluorescence quenching efficiency towards Fe3+, MnO4−, Cr2O72−, nitrofurantoin, and imidacloprid in aqueous media. A mechanism investigation suggested that the fluorescence quenching caused by the quenchers toward the sensor was due to the inner filter effect and the fluorescence resonance energy transfer effect in the fluorescent sensing process. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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Review

Jump to: Research

40 pages, 7283 KiB  
Review
Recent Advances in Low Valent Thorium and Uranium Chemistry
by Nikolaos Tsoureas and Ioannis Vagiakos
Inorganics 2024, 12(11), 275; https://doi.org/10.3390/inorganics12110275 - 24 Oct 2024
Cited by 2 | Viewed by 8068
Abstract
The synthesis, isolation, and characterisation of well-defined low-valent actinide complexes are reviewed with a main focus on compounds featuring uranium and thorium metal centres in formal oxidation states ≤ +3. The importance of the ligand environment in enabling access to these highly reactive [...] Read more.
The synthesis, isolation, and characterisation of well-defined low-valent actinide complexes are reviewed with a main focus on compounds featuring uranium and thorium metal centres in formal oxidation states ≤ +3. The importance of the ligand environment in enabling access to these highly reactive species, as well as its influence on ground state electronic configurations and their reactivity, are emphasised. Furthermore, we highlight cyclic voltammetry (C.V.) studies as a more widely used method that can guide the synthesis of these highly reducing species. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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