http://www.mdpi.com/journal/materials/special_issues/organomet-comp/ 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 Submission All papers should be submitted to materials@mdpi.com. To be published continuously until the deadline and papers will be listed together at the special website. Submitted papers should not have been published previously, nor be under consideration for publication elsewhere. All papers are refereed through a peer-review process. A guide for authors is available on the Instructions for Authors page. Materials is an international peer-reviewed quarterly journal published by MDPI. Review manuscripts: Before writing their manuscripts, potential authors of review articles should forward the title and a short abstract to materials@mdpi.com. We will then provide feedback on the suitability of the topic. Open Access publication fees are 300 CHF per paper. English correction fees and/or formatting fees (250 CHF) will be added in certain cases (550 CHF per paper for those papers that require extensive additional formatting and/or English corrections). Starting 1 January 2010, Article Processing Charges are of 800 CHF per accepted article for Materials http://www.mdpi.com/1996-1944/3/5/3407/ 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. http://www.mdpi.com/1996-1944/3/5/3407/ Tue, 25 May 2010 00:00:00 CEST Materials 2010-05-25 3 5 Review 3407 3429 1996-1944 Of Chains and Rings: Synthetic Strategies and Theoretical Investigations for Tuning the Structure of Silver Coordination Compounds and Their Applications 2010-05-25 doi: 10.3390/ma3053407 Slenters Sagué Brunetto Zuber Fleury Mirolo Robin Meuwly Gordon Landmann Daniels Fromm http://www.mdpi.com/1996-1944/3/4/2516/ 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. http://www.mdpi.com/1996-1944/3/4/2516/ Mon, 05 Apr 2010 00:00:00 CEST Materials 2010-04-05 3 4 Article 2516 2535 1996-1944 The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study 2010-04-05 doi: 10.3390/ma3042516 Yumura Hasegawa Itadani Kobayashi Kuroda http://www.mdpi.com/1996-1944/3/4/2447/ 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. http://www.mdpi.com/1996-1944/3/4/2447/ Tue, 30 Mar 2010 00:00:00 CEST Materials 2010-03-30 3 4 Article 2447 2462 1996-1944 New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity 2010-03-30 doi: 10.3390/ma3042447 Fritsch Rose Wollmann Böhlmann Kaskel http://www.mdpi.com/1996-1944/3/3/2141/ 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. http://www.mdpi.com/1996-1944/3/3/2141/ Mon, 22 Mar 2010 00:00:00 CET Materials 2010-03-22 3 3 Review 2141 2171 1996-1944 Nitrogen Doped Carbon Nanotubes from Organometallic Compounds: A Review 2010-03-22 doi: 10.3390/ma3032141 Nxumalo Coville http://www.mdpi.com/1996-1944/3/3/2087/ 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. http://www.mdpi.com/1996-1944/3/3/2087/ Fri, 19 Mar 2010 00:00:00 CET Materials 2010-03-19 3 3 Review 2087 2140 1996-1944 Recent Progress on Enyne Metathesis: Its Application to Syntheses of Natural Products and Related Compounds 2010-03-19 doi: 10.3390/ma3032087 Mori http://www.mdpi.com/1996-1944/3/2/1172/ 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. http://www.mdpi.com/1996-1944/3/2/1172/ Mon, 15 Feb 2010 00:00:00 CET Materials 2010-02-15 3 2 Article 1172 1185 1996-1944 Thermal Stability and Sublimation Pressures of Some Ruthenocene Compounds 2010-02-15 doi: 10.3390/ma3021172 M. Aslam Siddiqi Rehan A. Siddiqui Burak Atakan Nina Roth Heinrich Lang http://www.mdpi.com/1996-1944/3/2/1125/ 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. http://www.mdpi.com/1996-1944/3/2/1125/ Wed, 10 Feb 2010 00:00:00 CET Materials 2010-02-10 3 2 Article 1125 1137 1996-1944 Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes 2010-02-10 doi: 10.3390/ma3021125 Florian Lunzer Christoph Marschner http://www.mdpi.com/1996-1944/3/2/1049/ 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. http://www.mdpi.com/1996-1944/3/2/1049/ Tue, 09 Feb 2010 00:00:00 CET Materials 2010-02-09 3 2 Review 1049 1088 1996-1944 Organometallic Routes into the Nanorealms of Binary Fe-Si Phases 2010-02-09 doi: 10.3390/ma3021049 Manoj K. Kolel-Veetil Teddy M. Keller http://www.mdpi.com/1996-1944/3/2/1015/ 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. http://www.mdpi.com/1996-1944/3/2/1015/ Wed, 03 Feb 2010 00:00:00 CET Materials 2010-02-03 3 2 Article 1015 1030 1996-1944 Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes 2010-02-03 doi: 10.3390/ma3021015 Vanessa Tabernero Claudimar Camejo Pilar Terreros María Dolores Alba Tomás Cuenca http://www.mdpi.com/1996-1944/3/2/841/ 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. http://www.mdpi.com/1996-1944/3/2/841/ Mon, 01 Feb 2010 00:00:00 CET Materials 2010-02-01 3 2 Review 841 862 1996-1944 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 2010-02-01 doi: 10.3390/ma3020841 Michael G. Gardiner Damien N. Stringer http://www.mdpi.com/1996-1944/2/4/1558/ 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. http://www.mdpi.com/1996-1944/2/4/1558/ Wed, 21 Oct 2009 00:00:00 CEST Materials 2009-10-21 2 4 Review 1558 1598 1996-1944 Organotin Polyethers as Biomaterials 2009-10-21 doi: 10.3390/ma2041558 Charles E. Carraher Michael R. Roner http://www.mdpi.com/1996-1944/2/3/978/ 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. http://www.mdpi.com/1996-1944/2/3/978/ Thu, 20 Aug 2009 00:00:00 CEST Materials 2009-08-20 2 3 Article 978 991 1996-1944 Synthesis of Aryliron Complexes [CpFe(CO)2Ar] by Palladium-Catalyzed Reactions of [CpFe(CO)2I] with Arylzinc, -Boron, or -Indium Reagents 2009-08-20 doi: 10.3390/ma2030978 Shigeo Yasuda Yoshihiro Asada Hideki Yorimitsu Koichiro Oshima