Oxo-bridge scenario behind single-site water-oxidation catalysts.

High-oxidation-state decay of mononuclear complexes [RuTB(H2O)](2+) (X(2+), where B = 2,2'-bpy or bpy for X = 1; B = 5,5'-F2-bpy for X = 2; B = 6,6'-F2-bpy for X = 3; T = 2,2':6',2″-terpyridine) oxidized with a large excess of Ce(IV) generates a manifold of polynuclear oxo-bridged complexes. These include the following complexes: (a) dinuclear [TB-Ru(IV)-O-Ru(IV)-(T)(O)OH2](2+) (1-dn(4+)), [TB-Ru(III)-O-Ru(III)-T(MeCN)2](4+) (1-dn-N(4+)), and {[Ru(III)(trpy)(bpy)]2(µ-O)}(4+) (1-dm(4+)); (b) trinuclear {[Ru(III)(trpy)(bpy)(µ-O)]2Ru(IV)(trpy)(H2O)}(ClO4)5(6+) (1-tr(6+)) and {[Ru(III)(trpy)(bpy)(µ-O)]2Ru(IV)(pic)2}(ClO4)4 (1-tr-P(4+), where P is the 2-pyridinecarboxylate anion); and (c) tetranuclear [TB-Ru(III)-O-TRu(IV)(H2O)-O-TRu(IV)(H2O)-O-Ru(III)-TB](8+) (1-tn(8+)), [TB-Ru(III)-O-TRu(IV)(AcO)-O-TRu(IV)(AcO)-O-Ru(III)-TB](6+) (1-tn-Ac(6+)), and [TB-Ru(II)-O-TRu(IV)(MeCN)-O-TRu(IV)(MeCN)-O-Ru(II)-TB](6+) (1-tn-N(6+)). These complexes have been characterized structurally by single-crystal X-ray diffraction analysis, and their structural properties were correlated with their electronic structures. Dinuclear complex 1-dm(4+) has been further characterized by spectroscopic and electrochemical techniques. Addition of excess Ce(IV) to 1-dm(4+) generates dioxygen in a catalytic manner. However, resonance Raman spectroscopy points to the in situ formation of 1-dn(4+) as the active species.

Small bite-angle P-OP ligands for asymmetric hydroformylation and hydrogenation.

A series of small bite-angle phosphine-phosphite (P-OP) ligands have been synthesized by a two-step method. The key intermediate was prepared by an unprecedented asymmetric carbonyl reduction of a phosphamide using the CBS (Corey-Bakshi-Shibata) catalyst. The topology of these ligands (a configurationally stable stereogenic carbon with two heteroatom substituents) and their small bite-angle (created by the close proximity of the two ligating groups to the metal center) together provide a rigid asymmetric environment around this center, enabling high stereoselectivity in hydroformylations and hydrogenations of standard substrates.

Mononuclear ruthenium-water oxidation catalysts: discerning between electronic and hydrogen-bonding effects.

New mononuculear complexes of the general formula [Ru(trpy)(n,n'-F2-bpy)X](m+) [n = n' = 5, X = Cl (3(+)) and H2O (5(2+)); n = n' = 6, X = Cl (4(+)) and H2O (6(2+)); trpy is 2,2':6':2"-terpyridine] have been prepared and thoroughly characterized. The 5,5'- and 6,6'-F2-bpy ligands allow one to exert a remote electronic perturbation to the ruthenium metal center, which affects the combination of species involved in the catalytic cycle. Additionally, 6,6'-F2-bpy also allows through-space interaction with the Ru-O moiety of the complex via hydrogen interaction, which also affects the stability of the different species involved in the catalytic cycle. The combination of both effects has a strong impact on the kinetics of the catalytic process, as observed through manometric monitoring.

Allosteric P═O-based receptors for dicarboxylic acids.

The synthesis of new P═O-disubstituted receptors with appended crown ethers and their properties as receptors for dicarboxylic acids have been studied. High affinities have been observed (oxalic and malonic acids with 4-, 5-, 6-, or 8-crown ethers). Binding of a cationic effector within the crown ether unit resulted in a positive "allosteric" effect, which has been determined to be K(rel) = 7 in the best case (binding of malonic acid with Li(+) @ rac-3b).

Dioxirane mediated asymmetric epoxidations: stereochemical studies via isotopic labeling.

A study, via isotopic labeling, of the stereoselective processes in a Shi-type epoxidation, has revealed that the chiral platform provided by the catalyst mediates the transfer of the pro-S "O" of the related dioxirane species to the alkene in a doubly stereoselective manner.

Practical synthesis of Shi's diester fructose derivative for catalytic asymmetric epoxidation of alkenes.

[reaction: see text] A practical synthesis of Shi's diester 3 for catalytic asymmetric epoxidations has been developed. The catalyst has been prepared in multigram quantities from D-fructose in four steps with a 66% overall yield. Efficiency, cost, and selectivity aspects of the reagents involved for its preparation have been taken care of during its preparation. The workup procedures have been simplified to the bare minimum, rendering a very practical preparation method. The well-known high efficiency of this catalyst 3 in the epoxidation of alpha,beta-unsaturated carbonyl compounds has also proved to be high in unfunctionalized alkenes.

Spirocyclopropanated bicyclopropylidenes: straightforward preparation, physical properites, and chemical transformations.

Perspirocyclopropanated bicyclopropylidene (6) was prepared in three steps from 7-cyclopropylidenedispiro[2.0.2.1]heptane (4) (24% overall) or, more efficiently, through dehalogenative coupling of 7,7-dibromo[3]triangulane (15) (82%). This type of reductive dimerization turned out to be successful for the synthesis of (E)- and (Z)-bis(spiropentylidene) 14 (67%) and even of the "third-generation" spirocyclopropanated bicyclopropylidene 17 (17% overall from 15). Whereas the parent bicyclopropylidene 1 dimerized at 180 degrees C to yield [4]rotane, dimerization of 6 at 130 degrees C under 10 kbar pressure occured only with opening of one three-membered ring to yield the polyspirocyclopropanated (cyclopropylidene)cyclopentane derivative 19 (34% yield), and at the elevated temperature the polyspirocyclopropanated 2-cyclopropylidene[3.2.2]propellane derivative 20 (25 % yield). Perspirocyclopropanated bicyclopropylidene 6 and the "third-generation" bicyclopropylidene 17 gave addition of bromine, hydrogen bromide, and various dihalocarbenes without rearrangement. The functionally substituted branched [7]triangulane 28 and branched dichloro-C2v-[15]triangulane 32 were used to prepare the perspirocyclopropanated [3]rotane (D3h-[10]triangulane) 49 (six steps from 6, 1.4% overall yield) and the C2v-[15]triangulane 51 (two steps from 17, 41% overall). Upon catalytic hydrogenation, the perspirocyclopropanated bicyclopropylidene 6 yielded 7,7'-bis(dispiro[2.0.2.]-heptyl) (52) and, under more forcing conditions, 1,1'-bis(2,2,3,3-tetramethylcyclopropyl) (53). The bromofluorocarbene adduct 33 of 17 reacted with butyllithium to give the unexpected polyspirocyclopropanated 1,4-di-n-butyl-2-cyclopropylidenebicyclo[2.2.0]hexane derivative 37 as the main product (55% yield) along with the expected "third-generation" perspirocyclopropanated dicyclopropylidenemethane 38 (21% yield). Mechanistic aspects of this and the other unusual reactions are discussed. The structures of all new unusual hydrocarbons were proven by X-ray crystal structure analyses, and the most interesting structural and crystal packing features are presented.

NO-independent stimulators of soluble guanylate cyclase.

SARs around a novel type of guanylate cyclase stimulator which act by a mechanism different from classical NO-donors are described. Several pyrazolopyridinylpyrimidines are shown to relax aortic rings and revealed a long-lasting blood pressure lowering effect in rats after oral application.