Shape and symmetry of heptacoordinate transition-metal complexes: structural trends

The stereochemistries of heptacoordinate transition-metal complexes are analyzed by using continuous symmetry and shape measures of their coordination spheres. The distribution of heptacoordination through the transition-metal series is presented based on structural database searches including organometallic and Werner-type molecular complexes, metalloproteins, and extended solids. The most common polyhedron seems to be the pentagonal bipyramid, while different preferences are found for specific families of compounds, as in the complexes with three or four carbonyl or phosphine ligands, which prefer the capped octahedron or the capped trigonal prism rather than the pentagonal bipyramid. The symmetry maps for heptacoordination are presented and shown to be helpful for detecting stereochemical trends. The maximal symmetry interconversion pathways between the three most common polyhedra are defined in terms of symmetry constants and a large number of experimental structures are seen to fall along those paths.     

The rich stereochemistry of eight-vertex polyhedra: a continuous shape measures study

A stereochemical study of polyhedral eight-vertex structures is presented, based on continuous shape measures (CShM). Reference polyhedra, shape maps, and minimal-distortion interconversion paths are presented for eight-vertex polyhedral and polygonal structures within the CShM framework. The application of these stereochemical tools is analyzed for several families of experimental structures: 1) coordination polyhedra of molecular transition-metal coordination compounds, classified by electron configuration and ligands; 2) edge-bonded polyhedra, including cubane structures, realgar, and metal clusters; 3) octanuclear transition-metal supramolecular architectures; and 4) coordination polyhedra in extended structures in inorganic solids. Structural classification is shown to be greatly facilitated by these tools, and the detection of less common structures, such as the gyrobifastigium, is straightforward.     

Shape and spin state in four-coordinate transition-metal complexes: the case of the d(6) configuration

Generalized polyhedral interconversion coordinates are defined within the framework of Avnir's continuous shape measures. The application of such interconversion coordinates to the study of the potential energy surfaces that define the stereochemical choice in four-coordinate transition metal complexes with different spin states is presented, and the correlation between potential energy curves and distribution of experimental structures along the tetrahedron to square interconversion path is shown for the case of the d(6) transition-metal complexes.     

Continuous symmetry measures for complex symmetry group

Symmetry is a fundamental property of nature, used extensively in physics, chemistry, and biology. The Continuous symmetry measures (CSM) is a method for estimating the deviation of a given system from having a certain perfect symmetry, which enables us to formulate quantitative relation between symmetry and other physical properties. Analytical procedures for calculating the CSM of all simple cyclic point groups are available for several years. Here, we present a methodology for calculating the CSM of any complex point group, including the dihedral, tetrahedral, octahedral, and icosahedral symmetry groups. We present the method and analyze its performances and errors. We also introduce an analytical method for calculating the CSM of the linear symmetry groups. As an example, we apply these methods for examining the symmetry of water, the symmetry maps of AB₄ complexes, and the symmetry of several Lennard‐Jones clusters. © 2014 Wiley Periodicals, Inc.     

Transition metal complexes coordinated by an NAD(P)H model compound and their enhanced hydride-donating abilities in the presence of a base

The ruthenium(II) and rhenium(I) complexes containing an NAD(P)H model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), as ligand, [Ru(tpy)(bpy)(BNAH)]2+ (1 a) and [Re(bpy)(CO)3(BNAH)]+ (1 b), were quantitatively produced by the reaction of the corresponding metal hydrido complexes with BNA(+) (1-benzylnicotinamidium cation). In the presence of base with pK(a) = 8.9, 1 a and 1 b have much greater reducing power than "free" BNAH. The oxidation potentials of 1 a in the absence and the presence of triethylamine were 0.55 V and -0.04 V, respectively, versus Ag/AgNO(3), whereas that of "free" BNAH was 0.30 V. Spectroscopic results clearly showed that the base extracts a proton from the carbamoyl group on 1 a and 1 b to give the deprotonated BNAH coordinating to the transition-metal complexes [Ru(tpy)(bpy)(BNAH-H+)]+ (3 a) and [Re(bpy)(CO)3(BNAH-H+)] (3 b); this deprotonation underlies the enhancement in reducing ability. The deprotonated forms 3 a and 3 b can efficiently reduce other NAD(P) models to give the corresponding 1,4-dihydro form, resulting in the deprotonated BNA+ being coordinated to the metal complexes [Ru(tpy)(bpy)(BNA(+)-H+)]2+ (2 a) and [Re(bpy)(CO)3(BNA+-H+)]+ (2 b); "free" BNAH and the protonated adducts 1 a and 1 b cannot act in this way. X-ray crystallography was performed on the PF6- salt of 2 a, and showed that the deprotonated nitrogen atom on the carbamoyl group coordinates to the ruthenium(II) metal center with a bond length of 2.086(3) Angstroms. Infrared spectral data suggested that the deprotonated carbamoyl group on the reduced forms 3 a and 3 b is converted to the imido group, and that the oxygen atom coordinates to the metal center.     

Spontaneous formation of heteroligated PtII complexes with chelating hemilabile ligands

The spontaneous formation of the heteroligated complex [PtCl(kappa(2)-Ph(2)PCH(2)CH(2)SMe)(Ph(2)PCH(2)CH(2)SPh)]Cl (8 a) by a novel ligand rearrangement process has been observed. By using the weak-link approach, the relative arrangement of the alkyl and aryl groups can be controlled by abstraction of chloride from 8 a to form the closed complex [Pt(kappa(2)-Ph(2)PCH(2)CH(2)SMe)(kappa(2)-Ph(2)PCH(2)CH(2)SPh)][BF(4)](2) (5) and reopening using halide ions to form semi-open complexes [PtX(kappa(2)-Ph(2)PCH(2)CH(2)SMe)(Ph(2)PCH(2)CH(2)SPh)]BF(4) (8 b; X=Cl(-)) and (8 c; X=I(-)). Analogous procedures using Ph(2)PCH(2)CH(2)SMe and 1,4-(Ph(2)PCH(2)CH(2)S)(2)C(6)H(4) lead to heteroligated bimetallic complexes 7 and 9, illustrating that this ligand rearrangement process can be used as a tool for the assembly of complementary metallosupramolecular structures.     

α‐Cationic Phosphines: Synthesis and Applications

In coordination chemistry, typical ancillary ligands are anionic or neutral species. Cationic ones are exceptions and, when used, the positively charged groups are normally attached to the periphery and not close to the donating atom. However, this concept article highlights a series of recent experimental, as well as theoretical results, suggesting that the utility in catalysis of cationic phosphines with no spacer between the phosphorus atom and the positively charged group(s) has been largely overlooked. In fact, a growing number of studies indicate that, because of their specific architecture, these cationic ligands depict excellent π‐acceptor character that can exceed that of phosphites or polyfluorinated phosphines. This property has been used to increase the Lewis acidity of the metals they coordinate. Specifically, new extreme π‐acid catalysts, mainly based on Pt^II and Au^I, have been recently prepared and their superior performance demonstrated along several mechanistically distinct transformations. In this concept article the current state of the art is critically assessed and possible future directions of the topic discussed.     

Boron as a bridging ligand

The Lewis acidity of [(eta5-C5R5)Fe(CO)2(BX2)] (1: R = H, X = Cl) and the robust nature of the constituent Fe--B bond have been demonstrated by reaction with 4-methylpyridine to yield the corresponding Lewis acid-base adduct. These properties have subsequently been utilised in the construction of heterodinuclear bridging borylene, bridging boryl and mu(2)-boride complexes from analogues 3 (R = Me, X = Br) and 5 (R = Me, X = Cl). All the bimetallic species so formed exhibited unprecedented coordination modes for boron.     

Alternative Metals for Homogeneous Catalyzed Hydroformylation Reactions

Transition‐metal‐catalyzed hydroformylation reactions constitute one of the most powerful tools for C? C bond formation in organic synthesis and represent an outstanding example of the application of homogeneous catalysis on an industrial scale. This process allows for the straightforward conversion of inexpensive chemical feedstock into broadly applicable aldehydes, which serve as major building blocks for numerous chemical products. These products are highly valuable for the chemical industry and used as plasticizers, detergents, and surfactants on a million ton scale. Moreover, aldehydes serve as versatile chemical intermediates for the production of fine chemicals and pharmaceuticals. Currently, most of the bulk hydroformylation processes rely on rhodium‐based catalysts. The increasing demand and resulting high cost of this precious metal has resulted in alternative transition‐metal catalysts becoming highly desirable. The following Review summarizes the progress achieved utilizing Ru, Ir, Pd, Pt, and Fe catalysts in hydroformylation reactions.     

Proton-coupled electron transfer originating from excited states of luminescent transition-metal complexes

Proton-coupled electron transfer (PCET) is of fundamental importance for small-molecule activation processes, such as water splitting, CO(2)-reduction, or nitrogen fixation. Ideally, energy-rich molecules such as H(2), CH(3)OH, or NH(3) could be generated artificially using (solar) light as an energy input. In this context, PCETs originating directly from electronically excited states play a crucial role. A variety of transition-metal complexes have been used recently for fundamental investigations of this important class of reactions, and the key findings of these studies are reviewed in this article. The present minireview differs from other reviews on the subject of PCET in that it focuses specifically on reactions occurring directly from electronically excited states.     

Exploiting threefold symmetry in asymmetric catalysis: the case of tris(oxazolinyl)ethanes ("trisox")

Rotational molecular symmetry, modularity and other aspects of ligand design have played a role in the development of a new class of stereodirecting ligands. The use of highly symmetrical, stereodirecting ligands may reduce the number of transition states and diastereomeric reaction intermediates and, in favourable cases, this degeneration of alternative reaction pathways may lead to high stereoselectivity in catalytic reactions and greatly simplifies the analysis of such transformations. In this concept article, we describe the way in which these considerations have played a role in the development of a new class of stereodirecting ligands. Tris(oxazolinyl)ethanes ("trisox") have proved to be versatile ligand systems for the development of enantioselective catalysts of the d- and f-block metals employed in a wide range of catalytic conversions. These include Lewis acid catalysed transesterifications, C-C and C-N coupling reactions, the catalytic polymerisation of alpha-olefins as well as Pd-catalysed allylic alkylations. An overview of the current state of this field is given and the potential for further development will be highlighted.     

Enhancing electrophilic alkene activation by increasing the positive net charge in transition-metal complexes and application in homogeneous catalysis

Among a large variety of fine-tuning parameters for homogeneous catalysts the net charge of transition-metal complexes appear to be an interesting factor that considerably affects activation of substrates and catalytic activity in general. The electrophilicity of coordinated alkenes in transition-metal complexes can be strongly enhanced by increasing the positive net charge, resulting in strong carbocationic properties. Theoretical and experimental studies have shown that the alkene in cationic complexes is kinetically and thermodynamically more activated towards nucleophilic addition than in neutral complexes. The concept of increasing the positive complex charge is thought to be useful for the development of new catalysts for reactions in which alkenes or other unsaturated substrates are involved.     

Metal alkynyl sigma complexes: synthesis and materials

Metal alkynyl complexes hold a fascination for synthetic chemists, structural chemists, and materials scientists alike. Harnessing the unique overlap of metal and carbon orbitals is a challenge that can be overcome in many ways and hence, there are many synthetic routes toward M-C=C-bond-forming reactions that utilize a wide variety of transition-metal and alkynyl reagents. Some methods can be widely applied, while others are specific to a particular metal or compound. The linear geometry of the alkynyl unit and its pi-unsaturated character have led to metal alkynyls becoming attractive building blocks for molecular wires and polymeric organometallic materials, which can possess interesting properties, such as optical nonlinearity, luminescence, liquid crystallinity, and electrical conductivity. A unique, multifaceted approach, often combining talents from all three of the above chemical disciplines, has served as a driving force behind the intense research into the development of metal alkynyl sigma complexes, the progress of which, particularly in the last ten years, is summarized in this review.