This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

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Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

ion from a primary OH group of glyc-erol. 223,231 A similar mechanism was proposed manyyears ago for alcohol oxidation on Pt/C, involving asecond step, the transfer of a hydride ion to the Ptsurface (Scheme 11). 8,87,237 We consider it more feasible that the rate-deter-mining step is the cleavage of the C-H bond at theR-carbon atom. A similar mechanism is now generallyaccepted for Au electrodes (Scheme 12). 238 Despite thestructural differences between Au nanoparticles andan extended Au electrode surface, there are alsosimilarities, such as the critical role of aqueousalkaline medium and the absence of deactivation dueto decomposition products (CO and C x H y frag-ments). 239,240 An important question is the nature of active siteson Au nanoparticles. Electrooxidation of ethanol onAu nanoparticles supported on glassy carbon re-quired the partial coverage of Au surface by oxides. 241 Another analogy might be the model proposed for COoxidation. 219,242,243 According to this suggestion, theactive site consists of an ensemble of metallic Auatoms and a cationic Au

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

Magnetochemistry: advances in theory and experimentation

Ruthenium-Catalyzed Reactions for Organic Synthesis.

Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal oxide surfaces

Molecular and chain structures of four tetrakis(.mu.-propionato)-dirhodium(II) complexes with axial nitrogen-donor ligands

Magnetic exchange interactions in binuclear transition-metal complexes. 17. Benzidine and p-phenylenediamine, extended aromatic diamine bridging ligands in binuclear copper(II) 2,2',2''-triaminotriethylamine and vanadyl bis(hexafluoroacetylacetonate) complexes

Catalytic oxidative cleavage of vicinal diols and related oxidations by ruthenium pyrochlore oxides: new catalysts for low-temperature oxidations with molecular oxygen

Pyridine and pyrazine adducts of tetrakis(acetato)dichromium

The crystal and molecular structure of bis(L-methioninato)copper(II), Cu(L-Met)/sub 2/, Cu(C/sub 5/H/sub 10/NO/sub 2/S)/sub 2/, has been determined from single-crystal three-dimensional x-ray data collected by counter methods. The compound crystallizes as elongated blue six-sided plates in the space group P2/sub 1/(C/sub 2//sup 2/, No. 4) with Z = 2, a = 9.487 (5) A, b = 5.061 (3) A, c = 15.563 (8) A, ..beta.. = 92.46 (3)/sup 0/, d/sub calcd/ = 1.601 g/cm/sup 3/, and d/sub obsd/ = 1.60(1)g/cm/sup 3/. Least-squares refinement of 1191 reflections having F/sup 2/ greater than or equal to 3sigma(F/sup 2/) gave a conventional R factor of 0.046. There are no discrete molecules in the crystal; it consists of isolated sheets of Cu(II) ions with tetragonal N/sub 2/O/sub 4/ ligand sets formed by trans coordination of two L-methionine molecules. Additional interactions with carboxylate ions from neighboring methionine molecules lead to two apical Cu--O bonds and link the Cu(II) ions to form a carboxylate-bridged sheet structure. The structure of Cu(L-Met)/sub 2/ is compared with that reported by others for racemic Cu(D,L-Met)/sub 2/. Infrared spectra and magnetic properties of both complexes are presented and discussed. Effective magnetic moments of the racemic complex fell in the range 1.85 tomore » 1.90 ..mu../sub B/ at temperatures between 270 and 6.2/sup 0/K and followed Curie law behavior. Similarly, effective magnetic moments of Cu(L-Met)/sub 2/ fell in the range 1.76 to 1.87 ..mu../sub B/ at temperatures between 270 and approx. 13.5 K; below 13.5 K, the magnetic moment steadily decreased to 1.65 ..mu../sub B/ at 4.2/sup 0/K. ESR spectra of both polycrystalline complexes were measured at Q- and X-band frequencies over wide temperature ranges. Crystallographic similarities between the free methionine ligands and their complexes with Cu(II), Zn(II), and Cd(II) are presented and discussed.« less

Timothy R. Felthouse

Papers

Molecular and chain structures of four tetrakis(.mu.-propionato)-dirhodium(II) complexes with axial nitrogen-donor ligands

Magnetic exchange interactions in binuclear transition-metal complexes. 17. Benzidine and p-phenylenediamine, extended aromatic diamine bridging ligands in binuclear copper(II) 2,2',2''-triaminotriethylamine and vanadyl bis(hexafluoroacetylacetonate) complexes

Catalytic oxidative cleavage of vicinal diols and related oxidations by ruthenium pyrochlore oxides: new catalysts for low-temperature oxidations with molecular oxygen

Pyridine and pyrazine adducts of tetrakis(acetato)dichromium

Molecular structure and magnetic properties of trans-bis(L-methioninato)copper(II), Cu(C5H10NO2S)2