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Inorganics, Volume 7, Issue 3 (March 2019)

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Cover Story (view full-size image) Water channels are critical to the function of the oxygen-evolving complex (OEC) in photosystem II, [...] Read more.
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Open AccessArticle
Synthesis and Structural Characterization of Two New Main Group Element Carboranylamidinates
Received: 26 February 2019 / Revised: 11 March 2019 / Accepted: 11 March 2019 / Published: 13 March 2019
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Abstract
Two new main group element carboranylamidinates were synthesized using a bottom-up approach starting from o-carborane, ortho-C2B10H12 (1, = 1,2-dicarba-closo-dodecaborane). The first divalent germanium carboranylamidinate, GeCl[HLCy] (3, [HLCy [...] Read more.
Two new main group element carboranylamidinates were synthesized using a bottom-up approach starting from o-carborane, ortho-C2B10H12 (1, = 1,2-dicarba-closo-dodecaborane). The first divalent germanium carboranylamidinate, GeCl[HLCy] (3, [HLCy] = [o-C2B10H10C(NCy)(NHCy)], Cy = cyclohexyl), was synthesized by treatment of GeCl2(dioxane) with 1 equiv. of in situ-prepared Li[HLCy] (2a) in THF and isolated in 47% yield. In a similar manner, the first antimony(III) carboranylamidinate, SbCl2[HLiPr] (4, [HLiPr] = [o-C2B10H10C(NiPr)(NHiPr)]), was obtained from a reaction of SbCl3 with 1 equiv. of Li[HLiPr] in THF (56% yield). The title compounds were fully characterized by analytical and spectroscopic methods as well as single-crystal X-ray diffraction. Both compounds 3 and 4 are monomeric species in the solid state, and the molecular geometries are governed by a stereo-active lone pair at the metal centers. Full article
(This article belongs to the Special Issue Metal Complexes Containing Boron Based Ligands)
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Open AccessReview
Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood
Received: 6 January 2019 / Revised: 18 February 2019 / Accepted: 26 February 2019 / Published: 12 March 2019
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Abstract
In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions [...] Read more.
In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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Open AccessCommunication
Water Network Dynamics Next to the Oxygen-Evolving Complex of Photosystem II
Received: 1 February 2019 / Revised: 19 February 2019 / Accepted: 22 February 2019 / Published: 11 March 2019
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Abstract
The influence of the environment on the functionality of the oxygen-evolving complex (OEC) of photosystem II has long been a subject of great interest. In particular, various water channels, which could serve as pathways for substrate water diffusion, or proton translocation, are thought [...] Read more.
The influence of the environment on the functionality of the oxygen-evolving complex (OEC) of photosystem II has long been a subject of great interest. In particular, various water channels, which could serve as pathways for substrate water diffusion, or proton translocation, are thought to be critical to catalytic performance of the OEC. Here, we address the dynamical nature of hydrogen bonding along the water channels by performing molecular dynamics (MD) simulations of the OEC and its surrounding protein environment in the S1 and S2 states. Through the eigenvector centrality (EC) analysis, we are able to determine the characteristics of the water network and assign potential functions to the major channels, namely that the narrow and broad channels are likely candidates for proton/water transport, while the large channel may serve as a path for larger ions such as chloride and manganese thought to be essential during PSII assembly. Full article
(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)
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Open AccessArticle
Tuning the Linear and Nonlinear Optical Properties of Pyrene-Pyridine Chromophores by Protonation and Complexation to d10 Metal Centers §
Received: 17 January 2019 / Revised: 4 March 2019 / Accepted: 5 March 2019 / Published: 9 March 2019
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Abstract
The linear and second-order nonlinear optical (NLO) properties of two pyrene-pyridine chromophores, namely, 4-(pyren-1-yl)pyridine (L1) and 4-(2-(pyren-1-yl)ethyl)pyridine (L2), were investigated and modulated by performing protonation/deprotonation cycles or by complexation to d10 metal centers such as Zn(II) [...] Read more.
The linear and second-order nonlinear optical (NLO) properties of two pyrene-pyridine chromophores, namely, 4-(pyren-1-yl)pyridine (L1) and 4-(2-(pyren-1-yl)ethyl)pyridine (L2), were investigated and modulated by performing protonation/deprotonation cycles or by complexation to d10 metal centers such as Zn(II) and Cu(I) to form the monomeric [Zn(CH3CO2)2(L1)2] complex and the [CuI(L2)]n coordination polymer, respectively. The structures of L1, L2, [Zn(CH3CO2)2(L1)2] and [CuI(L2)]n were determined by means of single-crystal X-ray diffraction studies. The NLO response, measured by the electric-field-induced second harmonic generation (EFISH) technique, was positive for both chromophores and showed an inversion of the sign after exposure to HCl vapors. This process was completely reversible and the original values were restored by simple exposure to NH3 vapors. Coordination of L1 to Zn(II) also resulted in a negative NLO response, although smaller in magnitude compared to the protonated form, due to the weak Lewis acidity of the “Zn(CH3CO2)2” fragment. The results were also interpreted on the basis of DFT/TDDFT calculations. Full article
(This article belongs to the Special Issue Metal Complexes as Nonlinear Optical Molecular Materials)
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Open AccessArticle
Electronic Communication between Dithiolato-Bridged Diiron Carbonyl and S-Bridged Redox-Active Centres
Received: 31 January 2019 / Revised: 1 March 2019 / Accepted: 2 March 2019 / Published: 8 March 2019
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Abstract
The catalytic potential of linked redox centres is exemplified by the catalytic site of [FeFe]-hydrogenases, which feature a diiron subsite linked by a cysteinyl S atom to a 4Fe4S cube. The investigation of systems possessing similarly-linked redox sites is important because it provides [...] Read more.
The catalytic potential of linked redox centres is exemplified by the catalytic site of [FeFe]-hydrogenases, which feature a diiron subsite linked by a cysteinyl S atom to a 4Fe4S cube. The investigation of systems possessing similarly-linked redox sites is important because it provides a context for understanding the biological system and the rational design of abiological catalysts. The structural, electrochemical and spectroscopic properties of Fe2(CO)5(CH3C(CH2S)2CH2SPhNO2, I-bzNO2 and the aniline analogue, I-bzNH2, are described and IR spectroelectrochemical studies have allowed investigation of the reduction products and their reactions with CO and protons. These measurements have allowed identification of the nitrobenzenyl radical anion, quantification of the shifts of the (CO) bands on ligand-based reduction compared with NO2/NH2 exchange and protonation of the pendent ligand. The strength of thioether coordination is related to the electronic effects, where competitive binding studies with CO show that CO/thioether exchange can be initiated by redox processes of the pendent ligand. Stoichiometric multi electron/proton transfer reactions of I-bzNO2 localised on nitrobenzene reductions occur at mild potentials and a metal-centred reduction in the presence of protons does not lead to significant electrocatalytic proton reduction. Full article
(This article belongs to the Special Issue Binuclear Complexes)
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Open AccessReview
Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials
Received: 11 January 2019 / Revised: 25 February 2019 / Accepted: 27 February 2019 / Published: 7 March 2019
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Abstract
The structural design of nanosized electrocatalysts is extremely important for cathodic oxygen reduction reactions (ORR) and anodic oxidation reactions in small organic compounds in direct fuel cells. While Pt is still the most commonly used electrode material for ORR, the Pd electrocatalyst is [...] Read more.
The structural design of nanosized electrocatalysts is extremely important for cathodic oxygen reduction reactions (ORR) and anodic oxidation reactions in small organic compounds in direct fuel cells. While Pt is still the most commonly used electrode material for ORR, the Pd electrocatalyst is a promising alternative to Pt, because it exhibits much higher electrocatalytic activity towards formic acid electrooxidation, and the electrocatalytic activity of ORR on the Pd electrode is the higher than that of all other precious metals, except for Pt. In addition, the mass activity of Pt in a core–shell structure for ORR can be improved significantly by using Pd and Pd-based materials as core materials. Herein, we review various nanoscale Pd-based bimetallic, trimetallic and core–shell electrocatalysts for formic acid oxidation and ORR of polymer electrolyte fuel cells (PEFCs). This review paper is separated into two major topics: the electrocatalytic activity towards formic acid oxidation over various Pd-based electrocatalysts, and the activity of ORR on Pd-based materials and Pd core–Pt shell structures. Full article
(This article belongs to the Special Issue Palladium Catalysts: From Design to Applications)
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Open AccessArticle
Non-Covalent Interactions Involving Alkaline-Earth Atoms and Lewis Bases B: An ab Initio Investigation of Beryllium and Magnesium Bonds, B···MR2 (M = Be or Mg, and R = H, F or CH3)
Received: 30 January 2019 / Revised: 15 February 2019 / Accepted: 26 February 2019 / Published: 5 March 2019
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Abstract
Geometries, equilibrium dissociation energies (De), intermolecular stretching, and quadratic force constants (kσ) determined by ab initio calculations conducted at the CCSD(T)/aug-cc-pVTZ level of theory, with De obtained by using the complete basis set (CBS) extrapolation [CCSD(T)/CBS [...] Read more.
Geometries, equilibrium dissociation energies (De), intermolecular stretching, and quadratic force constants (kσ) determined by ab initio calculations conducted at the CCSD(T)/aug-cc-pVTZ level of theory, with De obtained by using the complete basis set (CBS) extrapolation [CCSD(T)/CBS energy], are presented for the B···BeR2 and B···MgR2 complexes, where B is one of the following Lewis bases: CO, H2S, PH3, HCN, H2O or NH3, and R is H, F or CH3. The BeR2 and MgR2 precursor molecules were shown to be linear and non-dipolar. The non-covalent intermolecular bond in the B···BeR2 complexes is shown to result from the interaction of the electrophilic band around the Be atom of BeR2 (as indicated by the molecular electrostatic potential surface) with non-bonding electron pairs of the base, B, and may be described as a beryllium bond by analogy with complexes such as B···CO2, which contain a tetrel bond. The conclusions for the B···MgR2 series are similar and a magnesium bond can be correspondingly invoked. The geometries established for B···BeR2 and B···MgR2 can be rationalized by a simple rule previously enunciated for tetrel-bonded complexes of the type B···CO2. It is also shown that the dissociation energy, De, is directly proportional to the force constant, kσ, in each B···MR2 series, but with a constant of proportionality different from that established for many hydrogen-bonded B···HX complexes and halogen-bonded B···XY complexes. The values of the electrophilicity, EA, determined from the De for B···BeR2 complexes for the individual Lewis acids, A, reveal the order A = BeF2 > BeH2 > Be(CH3)2—a result that is consistent with the −I and +I effects of F and CH3 relative to H. The conclusions for the MgR2 series are similar but, for a given R, they have smaller electrophilicities than those of the BeR2 series. A definition of alkaline-earth non-covalent bonds is presented. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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Open AccessArticle
1H NMR Relaxometric Analysis of Paramagnetic Gd2O3:Yb Nanoparticles Functionalized with Citrate Groups
Received: 31 January 2019 / Revised: 26 February 2019 / Accepted: 27 February 2019 / Published: 4 March 2019
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Abstract
Gd2O3 nanoparticles doped with different amount of Yb3+ ions and coated with citrate molecules were prepared by a cheap and fast co-precipitation procedure and proposed as potential “positive” contrast agents in magnetic resonance imaging. The citrate was used to [...] Read more.
Gd2O3 nanoparticles doped with different amount of Yb3+ ions and coated with citrate molecules were prepared by a cheap and fast co-precipitation procedure and proposed as potential “positive” contrast agents in magnetic resonance imaging. The citrate was used to improve the aqueous suspension, limiting particles precipitation. The relaxometric properties of the samples were studied in aqueous solution as a function of the magnetic field strength in order to evaluate the interaction of the paramagnetic ions exposed on the surface with the water molecules in proximity. The nanoparticles showed high relaxivity values at a high magnetic field with respect to the clinically used Gd3+-chelates and comparable to those of similar nanosytems. Special attention was also addressed to the investigation of the chemical stability of the nanoparticles in biological fluid (reconstructed human serum) and in the presence of a chelating agent. Full article
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Open AccessReview
Ferritin: A Platform for MRI Contrast Agents Delivery
Received: 13 January 2019 / Revised: 24 February 2019 / Accepted: 25 February 2019 / Published: 2 March 2019
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Abstract
The search for high relaxivities and increased specificity continues to be central to the development of paramagnetic contrast agents for magnetic resonance imaging (MRI). Ferritin, due to its unique surface properties, architecture, and biocompatibility, has emerged as a natural nanocage that can potentially [...] Read more.
The search for high relaxivities and increased specificity continues to be central to the development of paramagnetic contrast agents for magnetic resonance imaging (MRI). Ferritin, due to its unique surface properties, architecture, and biocompatibility, has emerged as a natural nanocage that can potentially help to reach both these goals. This review aims to highlight recent advances in the use of ferritin as a nanoplatform for the delivery of metal-based MRI contrast agents (containing Gd3+, Mn2+, or Fe2O3) alone or in combination with active molecules used for therapeutic purposes. The collected results unequivocally show that the use of ferritin for contrast agent delivery leads to more accurate imaging of cancer cells and a significantly improved targeted therapy. Full article
(This article belongs to the Special Issue MRI Contrast Agents)
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Open AccessArticle
Computational Characterization of Single-Electron Transfer Steps in Water Oxidation
Received: 15 January 2019 / Revised: 14 February 2019 / Accepted: 22 February 2019 / Published: 1 March 2019
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Abstract
The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional [...] Read more.
The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional theory (DFT) calculations on the reactivity of a specific copper complex active in water oxidation that reacts through two consecutive single-electron transfers. Both inner-sphere (through transition state location) and outer-sphere (through Marcus theory) mechanisms are analyzed. The first electron transfer is found to operate through outer-sphere, and the second one through inner-sphere. The current work proposes a scheme for the systematic study of single-electron transfer in water oxidation catalysis and beyond. Full article
(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)
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Open AccessReview
Designing Ruthenium Anticancer Drugs: What Have We Learnt from the Key Drug Candidates?
Received: 29 November 2018 / Revised: 6 February 2019 / Accepted: 13 February 2019 / Published: 1 March 2019
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Abstract
After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro [...] Read more.
After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro activity; however, we have yet to find a ruthenium complex that would be a viable alternative to platinum drugs currently used in the clinic. We aimed to explore what we have learned from the most prominent complexes in the area, and to challenge new concepts in chemical design. Particularly relevant are studies involving NKP1339, NAMI-A, RM175, and RAPTA-C, which have paved the way for current research. We explored the development of the ruthenium anticancer field considering that the mechanism of action of complexes no longer focuses solely on DNA interactions, but explores a diverse range of cellular targets involving multiple chemical strategies. Full article
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Open AccessReview
Metal Coordination Complexes as Redox Mediators in Regenerative Dye-Sensitized Solar Cells
Received: 12 December 2018 / Revised: 16 January 2019 / Accepted: 17 January 2019 / Published: 26 February 2019
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Abstract
Dye-sensitized solar cells (DSSCs) have attracted a substantial interest in the last 30 years for the conversion of solar power to electricity. An important component is the redox mediator effecting the transport of charge between the photoelectrode and the dark counter electrode (CE). [...] Read more.
Dye-sensitized solar cells (DSSCs) have attracted a substantial interest in the last 30 years for the conversion of solar power to electricity. An important component is the redox mediator effecting the transport of charge between the photoelectrode and the dark counter electrode (CE). Among the possible mediators, metal coordination complexes play a prominent role and at present are incorporated in several types of devices with a power conversion efficiency exceeding 10%. The present review, after a brief introduction to the operation of DSSCs, discusses at first the requirements for a successful mediator. Subsequently, the properties of various classes of inorganic coordination complexes functioning as mediators relevant to DSSC operation are presented and the operational characteristics of DSSC devices analyzed. Particular emphasis is paid to the two main classes of efficient redox mediators, the coordination complexes of cobalt and copper; however other less efficient but promising classes of mediators, notably complexes of iron, nickel, manganese and vanadium, are also presented. Full article
(This article belongs to the collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))
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Open AccessReview
Water Oxidation Catalysts: The Quest for New Oxide-Based Materials
Received: 22 January 2019 / Revised: 14 February 2019 / Accepted: 17 February 2019 / Published: 26 February 2019
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Abstract
The expected shortage of fossil fuels as well as the accompanying climate change are among the major challenges of the 21st century. A global shift to a sustainable energy landscape is, therefore, of utmost importance. Over the past few years, solar technologies have [...] Read more.
The expected shortage of fossil fuels as well as the accompanying climate change are among the major challenges of the 21st century. A global shift to a sustainable energy landscape is, therefore, of utmost importance. Over the past few years, solar technologies have entered the energy market and have paved the way to replace fossil-based energy sources, in the long term. In particular, electrochemical solar-to-hydrogen technologies have attracted a lot of interest—not only in academia, but also in industry. Solar water splitting (artificial photosynthesis) is one of the most active areas in contemporary materials and catalysis research. The development of low-cost, efficient, and stable water oxidation catalysts (WOCs) remains crucial for artificial photosynthesis applications, because WOCs still represent a major economical and efficient bottleneck. In the following, we summarize recent advances in water oxidation catalysts development, with selected examples from 2016 onwards. This condensed survey demonstrates that the ongoing quest for new materials and informed catalyst design is a dynamic and rapidly developing research area. Full article
(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)
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Open AccessArticle
Dinuclear Gold Complexes Supported by Wide Bite Angle Diphosphines for Preorganization-Induced Selective Dual-Gold Catalysis
Received: 29 January 2019 / Revised: 14 February 2019 / Accepted: 20 February 2019 / Published: 26 February 2019
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Abstract
The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual-gold catalysis is explored. Using the preorganizing abilities of well-known wide bite angle diphosphine ligands, DBFPhos and DPEPhos, dinuclear Au(I)–Au(I) complexes 1 and 2 are used as precursors to form [...] Read more.
The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual-gold catalysis is explored. Using the preorganizing abilities of well-known wide bite angle diphosphine ligands, DBFPhos and DPEPhos, dinuclear Au(I)–Au(I) complexes 1 and 2 are used as precursors to form well-defined monocationic species with either a chlorido- or acetylido-ligand bridging the two gold centers. These compounds are active catalysts for the dual-gold heterocycloaddition of a urea-functionalized alkyne, and the preorganization of both Au-centers affords efficient σ,π-activation of the substrate, even at high dilution, significantly outperforming benchmark mononuclear catalysts. Full article
(This article belongs to the Special Issue Binuclear Complexes)
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Open AccessArticle
Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond
Received: 29 January 2019 / Revised: 13 February 2019 / Accepted: 14 February 2019 / Published: 26 February 2019
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Abstract
In an attempt to expand the library of M2B5 bicapped trigonal-bipyramidal clusters with different transition metals, we explored the chemistry of [Cp*WCl4] with metal carbonyls that enabled us to isolate a series of mixed-metal tungstaboranes with an M [...] Read more.
In an attempt to expand the library of M2B5 bicapped trigonal-bipyramidal clusters with different transition metals, we explored the chemistry of [Cp*WCl4] with metal carbonyls that enabled us to isolate a series of mixed-metal tungstaboranes with an M2{B4M’} {M = W; M’ = Cr(CO)4, Mo(CO)4, W(CO)4} core. The reaction of in situ generated intermediate, obtained from the low temperature reaction of [Cp*WCl4] with an excess of [LiBH4·thf], followed by thermolysis with [M(CO)5·thf] (M = Cr, Mo and W) led to the isolation of the tungstaboranes [(Cp*W)2B4H8M(CO)4], 13 (1: M = Cr; 2: M = Mo; 3: M = W). In an attempt to replace one of the BH—vertices in M2B5 with other group metal carbonyls, we performed the reaction with [Fe2(CO)9] that led to the isolation of [(Cp*W)2B4H8Fe(CO)3], 4, where Fe(CO)3 replaces a {BH} core unit instead of the {BH} capped vertex. Further, the reaction of [Cp*MoCl4] and [Cr(CO)5·thf] yielded the mixed-metal molybdaborane cluster [(Cp*Mo)2B4H8Cr(CO)4], 5, thereby completing the series with the missing chromium analogue. With 56 cluster valence electrons (cve), all the compounds obey the cluster electron counting rules. Compounds 15 are analogues to the parent [(Cp*M)2B5H9] (M= Mo and W) that seem to have generated by the replacement of one {BH} vertex from [(Cp*W)2B5H9] or [(Cp*Mo)2B5H9] (in case of 5). All of the compounds have been characterized by various spectroscopic analyses and single crystal X-ray diffraction studies. Full article
(This article belongs to the Special Issue Binuclear Complexes)
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Open AccessArticle
Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine
Received: 20 December 2018 / Revised: 31 January 2019 / Accepted: 19 February 2019 / Published: 26 February 2019
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Abstract
Complexes of group III metals (rare earth and actinides) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (BTP) have been investigated by computational (DFT) and, in limited cases, by experimental (FT-IR, X-ray) techniques with the goal of determining the characteristics of metal–ligand interactions. The DFT calculations using the M062X [...] Read more.
Complexes of group III metals (rare earth and actinides) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (BTP) have been investigated by computational (DFT) and, in limited cases, by experimental (FT-IR, X-ray) techniques with the goal of determining the characteristics of metal–ligand interactions. The DFT calculations using the M062X exchange-correlation functional revealed that metal–ligand distances correlate with the ionic radii of the metals, in agreement with available X-ray diffraction results on the Sc, Y, La, U, and Pu complexes. A related blue-shift trend could be observed in seven characteristic bands in the IR spectra associated with metal–ligand vibrations. The computations uncovered considerable charge transfer interactions, particularly in the actinide complexes, as important covalent contributions to the metal–ligand bonding. The covalent character of the metal–ligand bonds decreases in the actinides, from U to Cm. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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Open AccessReview
Bond Forming Reactions Involving Isocyanides at Diiron Complexes
Received: 28 January 2019 / Revised: 12 February 2019 / Accepted: 14 February 2019 / Published: 26 February 2019
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Abstract
The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus [...] Read more.
The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus towards iron-assisted or iron-catalyzed reactions. Diiron complexes, taking advantage of peculiar activation modes and reaction profiles associated with multisite coordination, have the potential to compensate the lower activity of Fe compared to other transition metals, in order to activate CNR ligands. A number of reactions reported in the literature shows that diiron organometallic complexes can effectively assist and promote most of the “classic” isocyanide transformations, including CNR conversion into carbyne and carbene ligands, CNR insertion, and coupling reactions with other active molecular fragments in a cascade sequence. The aim is to evidence the potential offered by diiron coordination of isocyanides for the development of new and more sustainable synthetic strategies for the construction of complex molecular architectures. Full article
(This article belongs to the Special Issue Binuclear Complexes)
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