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Special Issue "Organometallic Compounds"

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (31 January 2010)

Special Issue Editor

Guest Editor
Prof. Dr. Jun Okuda

Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany
Website | E-Mail
Fax: +49 241 809 2644
Interests: organometallic chemistry and homogeneous catalysis; polyolefins; biodegradable polymers; new homogeneous catalysts

Special Issue Information

Dear Colleagues,

Organometallic compounds, molecules that contain at least one metal-carbon or metal-hydrogen bond, have had an enormous impact on the development of homogeneous catalysts. Such molecularly well-defined catalysts have revolutionized organic synthesis by achieving efficiency and selectivity not achieved before. Organometallic compounds have also influenced material synthesis: Areas that have profited from the ready availability of volatile, stoichiometrically precisely defined molecular compounds of the metallic elements including synthesis of materials (metals, alloys, semi-conductors) by vapor deposition, of new molecular magnetic and electro optical materials (non-linear optics), of metal-organic frameworks as gas adsorbents, of metal-containing polymers, and of metallomeogens. The usefulness of organometallic compounds also expands beyond homogeneous catalysts to molecular-defined supported catalysts which are expected to combine the precise mechanistic feature of homogeneous systems with the robustness of heterogeneous catalysts. Thus organometallic compounds are currently finding wider applications in material synthesis as well. This special issue invites contributions from areas where well-defined organometallic compounds contributed to the area of advanced material synthesis.

Prof. Dr. Jun Okuda
Guest Editor

Keywords

  • metal-carbon bond
  • MOCVD
  • non-linear optics
  • MOF
  • supported catalysts
  • conducting polymers
  • molecular magnets
  • metallomeogens

Published Papers (12 papers)

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Research

Jump to: Review

Open AccessArticle The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study
Materials 2010, 3(4), 2516-2535; doi:10.3390/ma3042516
Received: 31 January 2010 / Revised: 29 March 2010 / Accepted: 1 April 2010 / Published: 5 April 2010
Cited by 11 | PDF Full-text (1036 KB) | HTML Full-text | XML Full-text
Abstract
Large-scale density functional theory calculations (DFT) found various types of binding of an unsaturated hydrocarbon (C2H2 and C2H4) to a ZSM-5 zeolite extraframework copper cation. We employed the DFT calculations based on the B3LYP functional to
[...] Read more.
Large-scale density functional theory calculations (DFT) found various types of binding of an unsaturated hydrocarbon (C2H2 and C2H4) to a ZSM-5 zeolite extraframework copper cation. We employed the DFT calculations based on the B3LYP functional to obtain local minima of an unsaturated hydrocarbon adsorbed on one or two copper cations embedded inside ZSM-5, and then compared their stabilization energies. The DFT results show that the stabilization energies are strongly dependent on the copper coordination environment as well as configurations of two copper cations. Consequently, the inner copper-carbon bonds are influenced substantially by a nanometer-scale cavity of ZSM-5. Full article
(This article belongs to the Special Issue Organometallic Compounds)
Open AccessArticle New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity
Materials 2010, 3(4), 2447-2462; doi:10.3390/ma3042447
Received: 31 January 2010 / Accepted: 25 March 2010 / Published: 30 March 2010
Cited by 23 | PDF Full-text (452 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET) of up to 445 m2 g-1 and a good stability under
[...] Read more.
We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET) of up to 445 m2 g-1 and a good stability under ambient conditions resulting from a highly hydrophobic inner surface. They show good performance as heterogeneous catalysts in the cyanosylilation of benzaldehyde as a test reaction. Due to their catalytic activity, this class of materials might be able to replace common homogeneous element-organic and often highly toxic catalysts especially in the food industry. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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Open AccessArticle Thermal Stability and Sublimation Pressures of Some Ruthenocene Compounds
Materials 2010, 3(2), 1172-1185; doi:10.3390/ma3021172
Received: 11 December 2009 / Revised: 29 January 2010 / Accepted: 10 February 2010 / Published: 15 February 2010
Cited by 8 | PDF Full-text (547 KB) | HTML Full-text | XML Full-text
Abstract
We set out to study the use of a series of ruthenocenes as possible and promising sources for ruthenium and/or ruthenium oxide film formation.The thermal stability of a series of ruthenocenes, including (η5-C5H4R)(η5-C
[...] Read more.
We set out to study the use of a series of ruthenocenes as possible and promising sources for ruthenium and/or ruthenium oxide film formation.The thermal stability of a series of ruthenocenes, including (η5-C5H4R)(η5-C5H4R´)Ru (1), R = R´ = H (3), R = H, R´ = CH2NMe2 (5), R = H, R´= C(O)Me (6), R = R´ = C(O)Me (7), R = H, R´ = C(O)(CH2)3CO2H (8), R = H, R´ = C(O)(CH2)2CO2H (9), R = H, R´ = C(O)(CH2)3CO2Me (10), R = H, R´= C(O)(CH2)2CO2Me (11), R = R´ = SiMe3), (η5-C4H3O-2,4-Me2)2Ru (2), and (η5-C5H5-2,4-Me2)2Ru (4) was studied by thermogravimetry. From these studies, it could be concluded that 1–4, 6 and 9–11 are the most thermally stable molecules. The sublimation pressure of these sandwich compounds was measured using a Knudsen cell. Among these, the compound 11 shows the highest vapor pressure. Full article
(This article belongs to the Special Issue Organometallic Compounds)
Open AccessArticle Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes
Materials 2010, 3(2), 1125-1137; doi:10.3390/ma3021125
Received: 19 January 2010 / Revised: 29 January 2010 / Accepted: 9 February 2010 / Published: 10 February 2010
PDF Full-text (107 KB) | HTML Full-text | XML Full-text
Abstract
The Cp2ZrCl2/2 BuLi catalyzed co-polymerization of H2MeSiSiMeH2 and PhSiH3 was compared to the homo-polymerization of H2MeSiSiPhH2. In contrast to the co-polymerization, which gave molecular weights comparable to homo-polymerization of phenylsilane, the
[...] Read more.
The Cp2ZrCl2/2 BuLi catalyzed co-polymerization of H2MeSiSiMeH2 and PhSiH3 was compared to the homo-polymerization of H2MeSiSiPhH2. In contrast to the co-polymerization, which gave molecular weights comparable to homo-polymerization of phenylsilane, the reaction of 1-methyl-2-phenyldisilane yielded a partially cross-linked high molecular weight polymer with very broad molecular weight distribution. A higher reactivity of phenyl-substituted silicon atoms compared to methyl-substituted ones was detected. Stoichiometric reactions of some disilanes with the slow dehydropolymerization catalyst CpCp*Hf(Cl)Si(SiMe3)3 gave metal disilanyl intermediates with selectivities that reflect the observed polymerization behavior. Full article
(This article belongs to the Special Issue Organometallic Compounds)
Open AccessArticle Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes
Materials 2010, 3(2), 1015-1030; doi:10.3390/ma3021015
Received: 14 January 2010 / Revised: 27 January 2010 / Accepted: 1 February 2010 / Published: 3 February 2010
Cited by 6 | PDF Full-text (511 KB) | HTML Full-text | XML Full-text
Abstract
In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a
[...] Read more.
In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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Open AccessArticle Synthesis of Aryliron Complexes [CpFe(CO)2Ar] by Palladium-Catalyzed Reactions of [CpFe(CO)2I] with Arylzinc, -Boron, or -Indium Reagents
Materials 2009, 2(3), 978-991; doi:10.3390/ma2030978
Received: 17 July 2009 / Revised: 19 August 2009 / Accepted: 20 August 2009 / Published: 20 August 2009
Cited by 7 | PDF Full-text (529 KB) | HTML Full-text | XML Full-text
Abstract
Transmetalation between [CpFe(CO)2I] and arylzinc iodide-lithium chloride complexes proceeds in the presence of catalytic amounts of palladium acetate and N,N,N’,N’-tetramethyl-1,2-cyclohexanediamine to yield the corresponding aryliron complexes [CpFe(CO)2Ar]. Phenylation of [CpFe(CO)2I] also takes place when triphenylindium is used
[...] Read more.
Transmetalation between [CpFe(CO)2I] and arylzinc iodide-lithium chloride complexes proceeds in the presence of catalytic amounts of palladium acetate and N,N,N’,N’-tetramethyl-1,2-cyclohexanediamine to yield the corresponding aryliron complexes [CpFe(CO)2Ar]. Phenylation of [CpFe(CO)2I] also takes place when triphenylindium is used under similar conditions. Arylboronic acids undergo arylation in the presence of cesium carbonate and a palladium-N-heterocyclic carbene complex, PEPPSI. The present methods are useful for the facile synthesis of various functionalized [CpFe(CO)2Ar]. The products [CpFe(CO)2Ar] represent an interesting class of aryl metals that undergo several transformation. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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Review

Jump to: Research

Open AccessReview Of Chains and Rings: Synthetic Strategies and Theoretical Investigations for Tuning the Structure of Silver Coordination Compounds and Their Applications
Materials 2010, 3(5), 3407-3429; doi:10.3390/ma3053407
Received: 16 March 2010 / Revised: 14 May 2010 / Accepted: 17 May 2010 / Published: 25 May 2010
Cited by 36 | PDF Full-text (1729 KB) | HTML Full-text | XML Full-text
Abstract
Varying the polyethyleneglycol spacer between two (iso)-nicotinic groups of the ligand systems, a large structural variety of silver coordination compounds was obtained, starting with zero-dimensional ring systems, via one-dimensional chains, helices and double-helices to two-dimensional polycatenanes. Theoretical calculations help to understand their formation
[...] Read more.
Varying the polyethyleneglycol spacer between two (iso)-nicotinic groups of the ligand systems, a large structural variety of silver coordination compounds was obtained, starting with zero-dimensional ring systems, via one-dimensional chains, helices and double-helices to two-dimensional polycatenanes. Theoretical calculations help to understand their formation and allow predictions in some cases. These structures can be tuned by careful design of the ligand, the use of solvent and the counter ions, influencing also other important properties such as light stability and solubility. The latter is important in the context of biomedical applications, using silver compounds as antimicrobial agents. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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Open AccessReview Nitrogen Doped Carbon Nanotubes from Organometallic Compounds: A Review
Materials 2010, 3(3), 2141-2171; doi:10.3390/ma3032141
Received: 11 February 2010 / Revised: 1 March 2010 / Accepted: 15 March 2010 / Published: 22 March 2010
Cited by 54 | PDF Full-text (1171 KB) | HTML Full-text | XML Full-text
Abstract
Nitrogen doped carbon nanotubes (N-CNTs) have become a topic of increased importance in the study of carbonaceous materials. This arises from the physical and chemical properties that are created when N is embedded in a CNT. These properties include modified chemical reactivity and
[...] Read more.
Nitrogen doped carbon nanotubes (N-CNTs) have become a topic of increased importance in the study of carbonaceous materials. This arises from the physical and chemical properties that are created when N is embedded in a CNT. These properties include modified chemical reactivity and modified conductivity and mechanical properties. A range of methodologies have been devised to synthesize N-CNTs. One of the procedures uses a floating catalyst in which an organometallic complex is decomposed in the gas phase in the presence of a nitrogen containing reactant to give N-CNTs. Most studies have been limited to ferrocene, ring substituted ferrocene and Fe(CO)5. This review covers the synthesis (and properties) of N-CNTs and other shaped carbon nanomaterials (SCNMs) produced using organometallic complexes. It summarizes the effects that physical parameters such as temperature, pressure, gas flow rates, type and concentration of N source etc. have on the N-CNT type, size and yields as well as the nitrogen content incorporated into the tubes that are produced from organometallic complexes. Proposed growth models for N-CNT synthesis are also reported. Full article
(This article belongs to the Special Issue Organometallic Compounds)
Open AccessReview Recent Progress on Enyne Metathesis: Its Application to Syntheses of Natural Products and Related Compounds
Materials 2010, 3(3), 2087-2140; doi:10.3390/ma3032087
Received: 28 December 2009 / Revised: 26 February 2010 / Accepted: 16 March 2010 / Published: 19 March 2010
Cited by 43 | PDF Full-text (996 KB) | HTML Full-text | XML Full-text
Abstract
Olefin metathesis using ruthenium carbene complexes is a useful method in synthetic organic chemistry. Enyne metathesis is also catalyzed by these complexes and various carbo- and heterocycles could be synthesized from the corresponding enynes. Dienyne metathesis, cross enyne metathesis and ring-opening enyne metathesis
[...] Read more.
Olefin metathesis using ruthenium carbene complexes is a useful method in synthetic organic chemistry. Enyne metathesis is also catalyzed by these complexes and various carbo- and heterocycles could be synthesized from the corresponding enynes. Dienyne metathesis, cross enyne metathesis and ring-opening enyne metathesis have been further developed. Various complicated compounds, such as the natural products and the related biologically active substances, could be synthesized using these metatheses reactions. Skeletal reorganization using the transition metals and metallotropic rearrangement are also discussed. Full article
(This article belongs to the Special Issue Organometallic Compounds)
Open AccessReview Organometallic Routes into the Nanorealms of Binary Fe-Si Phases
Materials 2010, 3(2), 1049-1088; doi:10.3390/ma3021049
Received: 4 January 2010 / Revised: 26 January 2010 / Accepted: 5 February 2010 / Published: 9 February 2010
Cited by 12 | PDF Full-text (2741 KB) | HTML Full-text | XML Full-text
Abstract
The Fe-Si binary system provides several iron silicides that have varied and exceptional material properties with applications in the electronic industry. The well known Fe-Si binary silicides are Fe3Si, Fe5Si3, FeSi, a-FeSi2 and b-FeSi
[...] Read more.
The Fe-Si binary system provides several iron silicides that have varied and exceptional material properties with applications in the electronic industry. The well known Fe-Si binary silicides are Fe3Si, Fe5Si3, FeSi, a-FeSi2 and b-FeSi2. While the iron-rich silicides Fe3Si and Fe5Si3 are known to be room temperature ferromagnets, the stoichiometric FeSi is the only known transition metal Kondo insulator. Furthermore, Fe5Si3 has also been demonstrated to exhibit giant magnetoresistance (GMR). The silicon-rich b-FeSi2 is a direct band gap material usable in light emitting diode (LED) applications. Typically, these silicides are synthesized by traditional solid-state reactions or by ion beam-induced mixing (IBM) of alternating metal and silicon layers. Alternatively, the utilization of organometallic compounds with reactive transition metal (Fe)-carbon bonds has opened various routes for the preparation of these silicides and the silicon-stabilized bcc- and fcc-Fe phases contained in the Fe-Si binary phase diagram. The unique interfacial interactions of carbon with the Fe and Si components have resulted in the preferential formation of nanoscale versions of these materials. This review will discuss such reactions. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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Open AccessReview Dinitrogen and Related Chemistry of the Lanthanides: A Review of the Reductive Capture of Dinitrogen, As Well As Mono- and Di-aza Containing Ligand Chemistry of Relevance to Known and Postulated Metal Mediated Dinitrogen Derivatives
Materials 2010, 3(2), 841-862; doi:10.3390/ma3020841
Received: 23 December 2009 / Revised: 27 January 2010 / Accepted: 29 January 2010 / Published: 1 February 2010
Cited by 10 | PDF Full-text (681 KB) | HTML Full-text | XML Full-text
Abstract
This paper reviews the current array of complexes of relevance to achieving lanthanide mediated nitrogen fixation. A brief history of nitrogen fixation is described, including a limited discussion of successful transition metal facilitated nitrogen fixation systems. A detailed discussion of the numerous lanthanide-nitrogen
[...] Read more.
This paper reviews the current array of complexes of relevance to achieving lanthanide mediated nitrogen fixation. A brief history of nitrogen fixation is described, including a limited discussion of successful transition metal facilitated nitrogen fixation systems. A detailed discussion of the numerous lanthanide-nitrogen species relevant to nitrogen fixation are discussed and are related to the Chatt cycle for nitrogen fixation. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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Open AccessReview Organotin Polyethers as Biomaterials
Materials 2009, 2(4), 1558-1598; doi:10.3390/ma2041558
Received: 22 September 2009 / Revised: 13 October 2009 / Accepted: 19 October 2009 / Published: 21 October 2009
Cited by 23 | PDF Full-text (345 KB) | HTML Full-text | XML Full-text
Abstract
Organotin polyethers are easily synthesized employing interfacial polymerization systems involving the reaction of hydroxyl-containing Lewis bases and organotin halides. A wide variety of organotin-containing polymeric products have been synthesized including those derived from natural and synthetic polymers such as lignin, xylan, cellulose, dextran,
[...] Read more.
Organotin polyethers are easily synthesized employing interfacial polymerization systems involving the reaction of hydroxyl-containing Lewis bases and organotin halides. A wide variety of organotin-containing polymeric products have been synthesized including those derived from natural and synthetic polymers such as lignin, xylan, cellulose, dextran, and poly(vinyl alcohol). Others have been synthesized employing known drug diols such as dicumarol, DES, and dienestrol and a wide variety of synthetic diols. Included in these materials are the first water soluble organotin polymers. The organotin polyethers exhibit a wide range of biological activities. Some selectively inhibit a number of unwanted bacteria, including Staph. MRSA, and unwanted yeasts such as Candida albicans. Some also inhibit a variety of viruses including those responsible for herpes infections and smallpox. Others show good inhibition of a wide variety of cancer cell lines including cell lines associated with ovarian, colon, lung, prostrate, pancreatic and breast cancer. The synthesis, structural characterization, and biological characterization of these materials is described in this review. Full article
(This article belongs to the Special Issue Organometallic Compounds)
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