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Organometallic Compounds: Design, Synthesis and Application

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: 31 July 2025 | Viewed by 8587

Special Issue Editor

Institute of Chemistry, Chinese Academy of Sciences, Beijing, China
Interests: catalyst design; polyethylene; polyisoprene; mechanism; organometallic chemistry

Special Issue Information

Dear Colleagues,

This Special Issue aims to explore the multifaceted world of organometallic compounds, focusing on their design, synthesis, and diverse applications. Organometallic compounds, at the intersection of organic and inorganic chemistry, offer a rich playground for researchers to explore. The scope encompasses the rational design of novel organometallic complexes, including ligand design, metal coordination, and structural elucidation. Synthesis methodologies, ranging from traditional organic synthesis techniques to advanced organometallic methodologies, will be highlighted. Moreover, this Special Issue will showcase the broad range of applications for organometallic compounds across various fields, such as catalysis, materials science, medicinal chemistry, polymers, and beyond. From catalyzing key chemical transformations to serving as building blocks for innovative materials and polymers, organometallic compounds play a pivotal role in advancing modern science and technology. Contributions exploring strategies to combine theory and experiment techniques, as well as those addressing emerging trends and challenges in the field, are encouraged. Overall, this Special Issue aims to provide a comprehensive overview of the latest developments and future directions in organometallic chemistry.

Dr. Yanping Ma
Guest Editor

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Keywords

  • organometallic compounds
  • design and synthesis
  • transition metal complexes
  • catalysis
  • metal coordination
  • catalytic applications
  • mechanisms
  • organic–inorganic hybrid compounds

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Published Papers (9 papers)

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Research

Jump to: Review

23 pages, 8630 KiB  
Article
Finely-Tuned Bis(imino)pyridylcobalt Complexes Enhance Ethylene Polymerization: The Role of Bulky and Halogen Substituents
by Elizabeth Ogbe, Yanping Ma, Yizhou Wang, Jiahao Gao, Yang Sun and Wen-Hua Sun
Molecules 2025, 30(4), 859; https://doi.org/10.3390/molecules30040859 - 13 Feb 2025
Viewed by 515
Abstract
The bis(imino)pyridylcobalt complexes have been finely tuned through using the aniline derivative bearing a meta-chloro substituent, besides its ortho- and para-di(4-fluorophenyl)methyl and ortho-methyl substituents for the series of 2-[1-(3-chloro-4,6-bis((di(4-fluorophenyl)methyl)-2-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) chlorides (2,6-Me2Ph, Co1; 2,6-Et2Ph, Co2 [...] Read more.
The bis(imino)pyridylcobalt complexes have been finely tuned through using the aniline derivative bearing a meta-chloro substituent, besides its ortho- and para-di(4-fluorophenyl)methyl and ortho-methyl substituents for the series of 2-[1-(3-chloro-4,6-bis((di(4-fluorophenyl)methyl)-2-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) chlorides (2,6-Me2Ph, Co1; 2,6-Et2Ph, Co2; 2,6-iPr2Ph, Co3; 2,4,6-Me3Ph, Co4; and 2,6-Et2-4-MePh, Co5). The compounds were characterized using elemental analysis, 1H/13C NMR, FT-IR spectroscopy, and the single-crystal X-ray diffraction used in confirming the molecular structures of Co1, Co2, Co4, and Co5. The newly synthesized precatalysts, maintaining steric influences with the addition of an electron-withdrawing meta-chloro group, achieved higher activities along with better thermal stability, and controlled molecular weights of polyethylenes obtained. Upon activation with either MAO or MMAO, all catalysts exhibited remarkable activity for ethylene polymerization, for example, 9.2 × 106 g mol−1 h−1 by Co1 at 70 °C with 30 min and 18.0 × 106 g mol−1 h−1 by Co4 with the first 5 min. Co4 demonstrated exceptionally thermal stability with the peak activity of 8.9 × 106 g mol−1 h−1 at 70 °C and slightly decreased to 7.2 × 106 g mol−1 h−1 at 80 °C, and even maintained an activity of 1.6 × 106 g mol−1 h−1 at 100 °C. More importantly, all resultant polyethylenes were characterized as having vinyl-terminal and high-linear feature along with narrow dispersity; the molecular weights could be adapted in the ranges from 6.4 to 50.0 kg mol−1. In comparison with previous cobalt analogs, the current system performed better thermal stability and polymerization efficiency. Therefore, such robust complex catalysts are potentially considered for the polyethylene industry. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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20 pages, 5000 KiB  
Article
The Effect of Alkyl Substituents on the Formation and Structure of Homochiral (R*,R*)-[R2Ga(µ-OCH(Me)CO2R′)]2 Species—Towards the Factors Controlling the Stereoselectivity of Dialkylgallium Alkoxides in the Ring-Opening Polymerization of rac-Lactide
by Magdalena Kaźmierczak, Łukasz Dobrzycki, Maciej Dranka and Paweł Horeglad
Molecules 2025, 30(1), 190; https://doi.org/10.3390/molecules30010190 - 6 Jan 2025
Viewed by 742
Abstract
Building on our previous studies, which have demonstrated that homochiral propagating species—(R*,R*)-[Me2Ga(µ-OCH(Me)CO2R)]2—were crucial for the heteroselectivity of [Me2Ga(µ-OCH(Me)CO2Me)]2 in the ring-opening polymerization (ROP) of [...] Read more.
Building on our previous studies, which have demonstrated that homochiral propagating species—(R*,R*)-[Me2Ga(µ-OCH(Me)CO2R)]2—were crucial for the heteroselectivity of [Me2Ga(µ-OCH(Me)CO2Me)]2 in the ring-opening polymerization (ROP) of racemic lactide (rac-LA), we have investigated the effect of alkyl groups on the structure and catalytic properties of dialkylgallium alkoxides in the ROP of rac-LA. Therefore, we have isolated and characterized the rac-[R2Ga(µ-OCH(Me)CO2Me]2 (R = Et (1), iPr (2) and rac-[R2Ga(µ-OCH(Me)C5H4N]2 (R = Et (3), iPr (4)) complexes, to demonstrate the effect of alkyl groups on the chiral recognition induced the formation of the respective homochiaral species—(R*,R*)-[R2Ga(µ-OCH(Me)CO2Me)]2 and (R*,R*)-[R2Ga(µ-OCH(Me)C5H4N]2. Moreover, we have investigated the structure of (S,S)-[R2Ga(µ-OCH(Me)CO2Me]2 (R = Et ((S,S)-1, R = iPr ((S,S)-2,) and their catalytic activity in the ROP of rac-LA. With an increase in the bulkiness of alkyl substituents on gallium the following can be observed: (a) the tendency for the formation of homochiral complexes decreased, (b) the symmetry of homochiral (S,S)-[R2Ga(µ-OCH(Me)CO2Me]2 (M = Me, Et (S,S)-1), iPr (S,S)-2) changed, and both have resulted in (c) lower or no heteroselectivtity across these complexes in the ROP of rac-LA. Importantly, the results have confirmed the crucial role of the chiral-induced formation of homochiral asymmetric dimers on the heteroselectivity of dialkylgallium alkoxides in the ROP of rac-LA. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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12 pages, 3914 KiB  
Article
Synthesis of Branched Cyclo-Olefin Copolymers Using Neutral α-Sulfonate-β-Diimine Nickel Catalyst
by Donghui Li, Lixia Pei, Wenbo Du, Xieyi Xiao, Heng Gao, Handou Zheng and Haiyang Gao
Molecules 2025, 30(1), 157; https://doi.org/10.3390/molecules30010157 - 3 Jan 2025
Cited by 2 | Viewed by 698
Abstract
The homopolymerization of norbornene and the copolymerization of norbornene and ethylene were carried out using the neutral α-sulfonate-β-diimine nickel catalyst SD-Ni. The neutral α-sulfonate-β-diimine catalyst is highly active in the homopolymerization of norbornene, producing vinyl-addition polynorbornene [...] Read more.
The homopolymerization of norbornene and the copolymerization of norbornene and ethylene were carried out using the neutral α-sulfonate-β-diimine nickel catalyst SD-Ni. The neutral α-sulfonate-β-diimine catalyst is highly active in the homopolymerization of norbornene, producing vinyl-addition polynorbornene (PNB) with a high molecular weight. The copolymerization of norbornene (NB) and ethylene (E) using the catalyst SD-Ni was also investigated. The α-sulfonate-β-diimine catalyst SD-Ni shows distinctive catalytic copolymerization properties to produce high-molecular-weight E-NB copolymers with low norbornene incorporation. Importantly, microstructure analyses confirm that the resultant E-NB copolymers are branched cyclo-olefin copolymers (COCs) with branched polyethylene units. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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16 pages, 4292 KiB  
Article
Reactions of an Anionic Gallylene with Azobenzene or Azide Compounds Through C(sp2)–H and C(sp3)–H Activation
by Jinfeng Sun, Fangfeng Chen, Juan Liu, Yihu Zhang, Dongyu He, Vladimir A. Dodonov and Yanxia Zhao
Molecules 2024, 29(21), 5021; https://doi.org/10.3390/molecules29215021 - 24 Oct 2024
Viewed by 1090
Abstract
The activation of inert C–H bonds remains a challenge in current chemistry. Here, we report the excellent reactivity of the anionic gallylene species [LGa:][Na(THF)3] (L = [(2,6-iPr2C6H3)NC(CH3)]22−, 1 [...] Read more.
The activation of inert C–H bonds remains a challenge in current chemistry. Here, we report the excellent reactivity of the anionic gallylene species [LGa:][Na(THF)3] (L = [(2,6-iPr2C6H3)NC(CH3)]22−, 1) that allows the selective activation one ortho sp2 C–H bond of several azobenzene and azide derivatives at ambient temperature, with the transfer of the hydrogen atom to one of the nitrogen atoms. The process leads to the formation of the aryl amido products [LGa-κ2N,C-PhNN(H)(p-R-C6H3)][Na(solvent)3] (2, R = H solvent = DME (1,2-Dimethoxyethane); 3, R = –OMe, solvent = DME; 4, R = –NMe2 solvent = THF), [LGa-κ2N,C-(m-CH3-C6H4)NN(H)(m-CH3-C6H3)][Na(15-C-5)2] (5) with new Ga–C and Ga–N bonds. Moreover, 1 is also effective for the C–H activation of two azides RN3 (R = 2,4,6-Me3C6H2 or 2,6-iPr2C6H3), resulting in the formation of gallium amides [LGa(NH-2-(CH2)-4,6-Me2C6H2)][Na(15-C-5)2] (6) and [LGa(NH-2,6-iPr2C6H3)2][Na(THF)5] (7) through intra- or intermolecular sp3 C–H amination. Significantly, these reactions occur for the highly challenging activation of inert C(sp2)–H and C(sp3)–H bonds, thus demonstrating the excellent reactivity of the Ga(I) species 1. The products 27 were characterized by X-ray crystallography, 1H and 13C NMR, UV–vis spectroscopy, and density functional theory (DFT) calculations. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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11 pages, 2025 KiB  
Article
Ethylene/Styrene Copolymerization by (Me3SiC5H4)TiCl2(O-2,6-iPr2-4-RC6H2) (R = H, SiEt3)-MAO Catalysts: Effect of SiMe3 Group on Cp for Efficient Styrene Incorporation
by Tiantian Huang, Taiga Fujioka, Daisuke Shimoyama and Kotohiro Nomura
Molecules 2024, 29(18), 4473; https://doi.org/10.3390/molecules29184473 - 20 Sep 2024
Cited by 1 | Viewed by 1053
Abstract
The synthesis and structural analysis of (Me3SiC5H4)TiCl2(OAr) [OAr = O-2,6-iPr2-4-RC6H2; R = H, SiEt3] revealed that it exhibits higher catalytic activities than (tBuC [...] Read more.
The synthesis and structural analysis of (Me3SiC5H4)TiCl2(OAr) [OAr = O-2,6-iPr2-4-RC6H2; R = H, SiEt3] revealed that it exhibits higher catalytic activities than (tBuC5H4)TiCl2(OAr), Cp*TiCl2(OAr), with efficient comonomer incorporation in ethylene/styrene copolymerization in the presence of a methylaluminoxane (MAO) cocatalyst. The catalytic activity in the copolymerization increased upon increasing the charged styrene concentration along with the increase in the styrene content in the copolymers, whereas the activities of other catalysts showed the opposite trend. (Me3SiC5H4)TiCl2(O-2,6-iPr2C6H3) displayed the most suitable catalyst performance in terms of its activity and styrene incorporation, affording amorphous copolymers with styrene contents higher than 50 mol% (up to 63.6 mol%) and with random styrene incorporation confirmed by 13C-NMR spectra. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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18 pages, 2994 KiB  
Article
Intensive Cycloalkyl-Fused Pyridines for Aminopyridyl–Zinc–Heteroimidazoles Achieving High Efficiency toward the Ring-Opening Polymerization of Lactides
by Yun Wang, Wenjuan Zhang, Pengjiang Zhu, Wei You, Xiaopan Xue, Rui Wang, Yanping Ma and Wen-Hua Sun
Molecules 2024, 29(17), 4150; https://doi.org/10.3390/molecules29174150 - 31 Aug 2024
Viewed by 1295
Abstract
The model precatalyst sp3- and sp2-N dinitrogen-coordinated zinc–heteroimidazole has been used as an efficient catalyst for the ring-opening polymerization of cyclic esters. Subsequent to our exceptional active 5,6,7-trihydroquinolin-8-amine-zinc catalysts for the ring-opening polymerization (ROP) of ε-caprolactone, various pyridine-fused [...] Read more.
The model precatalyst sp3- and sp2-N dinitrogen-coordinated zinc–heteroimidazole has been used as an efficient catalyst for the ring-opening polymerization of cyclic esters. Subsequent to our exceptional active 5,6,7-trihydroquinolin-8-amine-zinc catalysts for the ring-opening polymerization (ROP) of ε-caprolactone, various pyridine-fused cycloalkanones (ring size from five to eight) are developed for the correspondent fused amine–pyridine derivatives and their zinc–heteroimidazole chloride complexes Zn1Zn8 (LZnCl2) bearing N-diphenylphosphinoethyl pendants. Activated with two equivalents of LiN(SiMe3)2, the title zinc complexes efficiently promote the ROP of L-lactide (L-LA) in situ; among them, Zn4/2Li(NSiMe3)2 catalyzed 500 equivalent L-LA at 80 °C with 92% conversion in 5 min (TOF: 5520 h−1). Under the same conditions, the catalytic efficiency for the ROP of rac-LA by Zn1Zn8/2Li(NSiMe3)2 was slightly lower than that for L-LA (highest TOF: 4440 h−1). In both cases, cyclooctyl-fused pyridyl–zinc complexes exhibited higher activity than others, while the cycloheptyl-fused zinc complexes showed the lowest activity. The microstructure analysis of the polymers showed they possessed a linear structure capped with CH3O as major and cyclic structure as minor. In this work, all the ligands and zinc complexes were well characterized by 1H/13C/31P NMR, FT-IR spectroscopy as well as elemental analysis. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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13 pages, 3670 KiB  
Article
Influence of Polytetrafluoroethylene Content, Compaction Pressure, and Annealing Treatment on the Magnetic Properties of Iron-Based Soft Magnetic Composites
by Mei Song, Fan Luo, Yajing Shang and Zhongxia Duan
Molecules 2024, 29(17), 4019; https://doi.org/10.3390/molecules29174019 - 25 Aug 2024
Cited by 1 | Viewed by 1015
Abstract
To improve the magnetic properties of iron-based soft magnetic composites (SMCs), polytetrafluoroethylene (PTFE) with excellent heat resistance, electrical insulation, and extremely high electrical resistivity was chosen as an insulating coating material for the preparation of iron-based SMCs. The effects of PTFE content, compaction [...] Read more.
To improve the magnetic properties of iron-based soft magnetic composites (SMCs), polytetrafluoroethylene (PTFE) with excellent heat resistance, electrical insulation, and extremely high electrical resistivity was chosen as an insulating coating material for the preparation of iron-based SMCs. The effects of PTFE content, compaction pressure, and annealing treatment on the magnetic properties of Fe/PTFE SMCs were investigated in detail. The results demonstrate that the PTFE insulating layer is successfully coated on the surface of iron powders, which effectively reduces the core loss, increases the resistivity, and improves the frequency stability and the quality factor. Under the combined effect of optimal PTFE content, compaction pressure, and annealing treatment, the iron-based SMCs exhibit a high effective permeability of 56, high saturation magnetization of 192.9 emu/g, and low total core losses of 355 mW/cm3 and 1705 mW/cm3 at 50 kHz for Bm = 50 mT and 100 mT. This work provides a novel insulating coating layer that optimizes magnetic properties and is advantageous for the development of iron-based SMCs. In addition, it also provides a comprehensive understanding of the relationship between process parameters and magnetic properties, which is of great guiding significance for scientific research and industrial production. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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Review

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25 pages, 8015 KiB  
Review
Metal Complexes of Bispidine Derivatives: Achievements and Prospects for the Future
by Altynay B. Kaldybayeva, Valentina K. Yu, Feyyaz Durap, Murat Aydemir and Khaidar S. Tassibekov
Molecules 2025, 30(5), 1138; https://doi.org/10.3390/molecules30051138 - 3 Mar 2025
Viewed by 662
Abstract
Multidentate bispidine ligands, including tetra-, penta-, hexa-, hepta-, and octadentate variants, exhibit strong coordination tendencies due to their intrinsic rigidity, significant reorganization potential, and ability to efficiently encapsulate metal ions. These structural attributes profoundly influence the thermodynamic stability, metal ion selectivity, redox behavior, [...] Read more.
Multidentate bispidine ligands, including tetra-, penta-, hexa-, hepta-, and octadentate variants, exhibit strong coordination tendencies due to their intrinsic rigidity, significant reorganization potential, and ability to efficiently encapsulate metal ions. These structural attributes profoundly influence the thermodynamic stability, metal ion selectivity, redox behavior, and spin-state configuration of the resulting complexes. Metal ions, in turn, serve as highly suitable candidates for coordination due to their remarkable kinetic inertness, rapid complex formation kinetics, and low redox potential. This review focuses on ligands incorporating the bispidine core (3,7-diazabicyclo[3.3.1]nonane) and provides an overview of advancements in the synthesis of metal complexes involving p-, d-, and f-block elements. Furthermore, the rationale behind the growing interest in bispidine-based complexes for applications in radiopharmaceuticals, medicinal chemistry, and organic synthesis is explored, particularly in the context of their potential for diagnostic and catalytic drug development. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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12 pages, 1727 KiB  
Review
Recent Advancements in the Synthesis of Functional Polyolefins by Non-Bridged Half-Titanocenes
by Yanjun Chen and Haiqian Dong
Molecules 2025, 30(1), 39; https://doi.org/10.3390/molecules30010039 - 26 Dec 2024
Viewed by 732
Abstract
Polyolefins are used widely due to their benefits such as being lightweight, chemical inertness, low cost, tunable properties, and easy processability. However, their nonpolar nature significantly limits their high-end applications. The non-bridged half-titanocenes exhibit remarkable catalytic activities with good comonomer incorporations in the [...] Read more.
Polyolefins are used widely due to their benefits such as being lightweight, chemical inertness, low cost, tunable properties, and easy processability. However, their nonpolar nature significantly limits their high-end applications. The non-bridged half-titanocenes exhibit remarkable catalytic activities with good comonomer incorporations in the olefin polymerization. The synthesis of functional polyolefins has attracted more and more attention recently. The non-bridged half-titanocenes have been used in the preparation of functional polyolefins, in particular the functional olefin copolymers. Herein, the recent advancements in the synthesis of functional polyolefins by non-bridged half-titanocenes were reviewed. The functional polyolefins have been synthesized by direct copolymerization of olefin with functional comonomers using half-titanocenes as precatalysts. In addition, polyolefins containing reactive groups could be synthesized by the olefin (co)polymerization using half-titanocenes as precatalysts. The functional polyolefins were synthesized successfully by the post-functionalization of polyolefin containing reactive groups. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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