Cubanes acidity

Tetrahedral [NHa]", [NH3(0H)]", [NF4]", H3NBF3 and innumerable other coordination complexes of NH3, NR3, en, edta, etc., including Mc3NO and sulfamic acid (H3NSO3). BN (layer structure and Zn blende-type), AIN (wurtzite-type), [PhAlNPh]4 (cubane-type)... 

Cram s open-chain model 229 Cram s rule 229, 233 Cram chelate model 229 Cram cyclic model 229 Cram-Felkin-Anh model 191,207, 236 f 246 cubane 12,318 cyanoacetic acid 636 f. cyanohydrin, protected 145, 150 f. cyclic carbonate protection 541 f., 657, 659 f., 666, 670 cyclization -,6-endo 734 -, 5-exo 733 f. 

This supramolecular approach has been used as a way to facilitate the crystallization of cuboidal aqua ions and to capture single intermediates present in complex solution mixtures. For example, [M3Q4Clx(H20)9.x] (Q = S, Se) supramolecular adducts have been isolated for x =1-5 from aqueous HCl solutions by varying the acid concentrations where the aggregates contain in each case only one of all possible isomers [46]. In addition to the hydrogen bonds, other kinds of interactions, namely C1---H20, C1---C1 and Q---Q contacts, are also involved in the network propagation. This supramolecular approach has also been efficiently employed for the crystallization of a large number of aqua complexes within the [M3M Q4] cubane-type family, where M is a transition or post-transition metal [47]. 

Pentacyclo[4.2.0.02 5.03 8.04 7]octane-l,2-dicarboxylic acid (Cubane-1,2-dicarboxylic acid)... 

Action of chlorine trifluoride causes incandescence [1]. Manganese dioxide catalytically decomposes powerful oxidising agents, often violently. Dropped into cone, hydrogen peroxide, the powdered oxide may cause explosion [2], Either the massive or the powdered oxide explosively decomposes 92% peroxomonosulfuric acid [3], and mixtures with chlorates ( oxygen mixture , heated to generate the gas) may react with explosive violence [4], Cuban pyrolusite can be used in place of potassium dichromate to promote thermal decomposition of potassium chlorate in match-head formulations [5],... 

Amino acid is one of the most important biological ligands. Researches on the coordination of metal-amino acid complexes will help us better understand the complicated behavior of the active site in a metal enzyme. Up to now many Ln-amino acid complexes [50] and 1 1 or 1 2 transition metal-amino acid complexes [51] with the structural motifs of mononuclear entity or chain have been synthesized. Recently, a series of polynuclear lanthanide clusters with amino acid as a ligand were reported (most of them display a Ln404-cubane structural motif) [52]. It is also well known that amino acids are useful ligands for the construction of polynuclear copper clusters [53-56], Several studies on polynuclear transition metal clusters with amino acids as ligands, such as [C03] [57,58], [Co2Pt2] [59], [Zn6] [60], and [Fe ] [61] were also reported. 

It is well-known, that in most carboxylic acid crystal structures, the conformation of the carboxyl group is synplanar and that the most frequent and dominant interlink is the syn-syn centrosymmetric dimer synthon, II. This synthon is found in nearly a third of all crystalline carboxylic acids, with or without any other functionality being present in the molecule, signifying robustness.1211 Against such a background, the crystal structures of 1,4-cubane-... 

R. J. Butcher, A. Bashir-Hashemi, R. Gilardi, Network hydrogen bonding the crystal and molecular structure of cubane-l,35,7-tetracarboxylic acid dihydrate , J. Chem. Cryst., 1997, 27, 99-107. 

These experiments have been applied to a variety of molecules, the predominant ones being strained organic molecules such as cubane, norbornane, cyclopropane, etc. [30-33]. Recently, van der Waals complexes of formic acid have been subjected to EMS spectroscopy [34]. 

Formation of benzoic acid has not been observed. These results clearly suggest that in the aerobic oxidation of neat ethylbenzene the cubane complexes cobalt(III) are involved as the catalytic species. 

Dinitrocubane (28) has been synthesized by Eaton and co-workers via two routes both starting from cubane-l,4-dicarboxylic acid (25). The first of these routes uses diphenylphos-phoryl azide in the presence of a base and tert-butyl alcohol to effect direct conversion of the carboxylic acid (25) to the tert-butylcarbamate (26). Hydrolysis of (26) with mineral acid, followed by direct oxidation of the diamine (27) with m-CPBA, yields 1,4-diiutrocubane (28). Initial attempts to convert cubane-l,4-dicarboxylic acid (25) to 1,4-diaminocubane (27) via a Curtins rearrangement of the corresponding diacylazide (29) were abandoned due to the extremely explosive nature of the latter. However, subsequent experiments showed that treatment of the acid chloride of cubane-l,4-dicarboxylic acid with trimethylsilyl azide allows the formation of the diisocyanate (30) without prior isolation of the dangerous diacylazide (29) from solution. Oxidation of the diisocyanate (30) to 1,4-dinitrocubane (28) was achieved with dimethyldioxirane in wet acetone. Dimethyldioxirane is also reported to oxidize both the diamine (27) and its hydrochloride salt to 1,4-dinitrocubane (28) in excellent yield. ... 

Eaton and co-workers also reported the synthesis of 1,3,5-trinitrocubane and 1,3,5,7-tetranitrocubane (39) ° The required tri- and tetra-substituted cubane precursors were initially prepared via stepwise substitution of the cubane core using amide functionality to permit ort/jo-lithiation of adjacent positions. The synthesis of precursors like cubane-1,3,5,7-tetracarboxylic acid was long and inefficient by this method and required the synthesis of toxic organomercury intermediates. Bashir-Hashemi reported an ingenious route to cubane-1,3,5,7-tetracarboxylic acid chloride (35) involving photochemical chlorocarbonylation of cubane carboxylic acid chloride (34) with a mercury lamp and excess oxalyl chloride. Under optimum conditions this reaction is reported to give a 70 8 22 isomeric mixture of 35 36 37... 

The energetic cubane-based nitramine (22) is also synthesized from the direct A-nitration of the parent amine using a mixture of trifluoroacetic anhydride and nitric acid. ... 

Eaton and co-workers ° synthesized the cubane-based dinitrourea (42) via iV-nitration of the cyclic urea (41) with nitric acid-acetic anhydride. Cubane-based nitramide (43) is prepared from the IV-nitration of the corresponding bis-amide with acetic anhydride-nitric acid. Bis-nitramine (44) is prepared from the IV-nitration of the corresponding diamine with TFAA-nitric acid. ... 

Cubane-1,2-dicarboxylic acid 12 (see Fig. 2.19), a precursor for 1,2-dihalocubanes was prepared from commercially available cubane-1,4-dicarboxylic acid in 65% yield. The other acids 14a and 14c were similarly prepared from the cubane-1,4-dicarboxylic acid 14b according to the literature procedures. 

A brief historical note on the structure of the iron-sulfur clusters in ferredoxins is relevant. After the first analytical results revealed the presence of (nearly) equimolar iron and acid-labile sulfur, it was clear that the metal center in ferredoxins did not resemble any previously characterized cofactor type. The early proposals for the Fe S center structure were based on a linear chain of iron atoms coordinated by bridging cysteines and inorganic sulfur (Blomstrom et al., 1964 Rabino-witz, 1971). While the later crystallographic analyses of HiPIP, PaFd, and model compounds (Herskovitz et al., 1972) demonstrated the cubane-type structure of the 4Fe 4S cluster, the original proposals have turned out to be somewhat prophetic. Linear chains of sulfide-linked irons are observed in 2Fe 2S ferredoxins and in the high-pH form of aconitase. Cysteines linked to several metal atoms are present in metallothionein. The chemistry of iron-sulfur clusters is rich and varied, and undoubtedly many other surprises await in the future. 

Linkage isomerizations, osmium, 37 335-339 Linked cubane clusters, Fe—S proteins, biological implications, 38 55-56 Linked macrocyclic ring systems, 45 75 dinuclear systems, 45 89-95 triaza ring systems, 45 76-87 Li—N—Li linkages, 37 100-101 Lipoxygenase, inhibitors, 36 41 Liquid-liquid extraction of metal ions, 9 1-80 with acidic P-based extractants, 9 34-48 with acidic P-based extractants dinuclear, 9 47-48 mononuclear, 9 34-47 with amines and amine oxides, 9 49-56 complexes in, 9 68-71 countercurrent extraction method, 9 15-25... 

Ferredoxins with 4Fe4S clusters are small, low potential electron carriers that function in bacterial electron transfer. Like the binuclear clusters, each tetranu-clear cluster can reversibly accept a single electron. The tetranuclear prosthetic group is a cubane with iron and acid-labile inorganic sulfide groups at alternate vertices the four iron atoms and the four sulfides form interpenetrating tetrahedra of slightly different sizes. 

The most spectacular examples of the wide applicability of this method are the elegant syntheses of strained cubane- and homocubanecarboxylic acid derivatives,52 which have partially been reviewed (Houben-Weyl, Vol. 4/4, pp 94-119). 

The bond dissociation energy (BDE) and acidity constant (p ) of cubane (Cub—H) have been determined experimentally by Eaton and co-workers (Hare, M. Emrick, T. Eaton, P. E. Kass, S. R, J. Am. Chem. Soc., 1997, 119, 237-238). The BDE is unusually high for a tertiary C—H bond, 427 kJ/mol, about 25 kJ/mol higher than in isobutane. The C—H bond is also quite acidic, comparable to the acidity of the N—H bond in ammonia, pK = 36, indicating an unusual stability for the anion... 

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