From a combination of chiral Mn(salen) struts and the tetratopic ligand tetrakis(4-carboxyphenyl)benzene, a large-pore, noncatenated metal-organic framework (MOF) material, MnSO-MOF, has been synthesized. Following solvent exchange with hydrophobic CHCl(3), treatment of MnSO-MOF with aqueous H(2)O(2) allowed for the selective demetalation of Mn(salen) struts at and near the surface of the cryst...

(Salen)Mn(III) catalysts show increased turnover numbers in the catalytic asymmetric epoxidation of conjugated olefins upon addition of bulky Lewis acids (LA) such as zinc tetraphenylporphyrin (ZnTPP). Up to 3-fold increase in total catalytic activity and at least a 20-fold increase in catalyst stability was observed with a (salen)Mn catalyst bearing pendant 5,5′-bis-pyridyl groups. This latter...

Chiral ruthenium(II)-salen complexes [RuII(salen)(PPh3)2] catalyse asymmetric aziridination of alkenes with up to 83% ees, asymmetric amidation of silyl enol ethers with up to 97% ees, and allylic amidation of cholesteryl acetates with good regioselectivity.

Several metal complexes of three different functionalized salen derivatives have been synthesized. The salens differ in terms of the electrostatic character and the location of the charges. The interactions of such complexes with DNA were first investigated in detail by UV-vis absorption titrimetry. It appears that the DNA binding by most of these compounds is primarily due to a combination of ...

The nature of the anionic ligand X (X = EtOSO3, BF4, Cl, Br, OSO2CF3, F or CN) in vanadium(V)salen complexes [V+ O(salen) X-] was found to have a significant influence on the catalytic activity of the complexes, but not on their enantioselectivities; with the complexes in which X = Cl or F being most active and the complex with X = OSO2CF3 being totally inactive.

During asymmetric cyanohydrin synthesis catalysed by vanadium(V)oxo(salen) complexes, the catalysts are reduced to vanadium(IV)oxo(salen) as determined by EPR spectroscopy; the reducing agent is cyanide which is oxidised to cyanogen via a non-radical mechanism.

Two-dimensional layered compounds with different counteranions, [{Mn(salen)}4C6](BF4)2·2(CH3OH) (1) and [{Mn(salen)}4C6](PF6)2·2(CH3OH) (2) (salen2- = N,N'-bis(salicylideneiminato), C62- = C6H12(COO)22-), were synthesized by assembling [Mn(salen)(H2O)]X (X- = BF4- and PF6-) and C6H12(CO2-)2 (C62-) in a methanol/2-propanol medium. The compounds have similar structures, which are composed of Mn(s...

The construction of novel (macrocyclic) multinuclear Co(III)salen catalysts is reported. Olefin metathesis has been used as a key construction tool for the multimetallic structures starting from versatile allyl-substituted salen scaffolds. The Co(III) complexes were tested in the hydrolytic kinetic resolution of (rac)-1,2-epoxyhexane and epoxide ring opening reactions using methanol as the nucl...

A series of cobalt salen complexes, where salen represents an N2O2 bis-Schiff-base bis-phenolate framework, are prepared, characterised and investigated for reversible-termination organometallic mediated radical polymerisation (RT-OMRP). The salen ligands contain a cyclohexane diimine bridge and systematically altered para-substituted phenoxide moieties as a method to examine the electronic imp...

Presented are density functional calculations on various Mn(salen) systems that are active catalysts in the epoxidation of olefins. Correlation of various structural properties such as Mn=O bond strengths, atomic charges, and C-O distances of evolving bonds in transition state geometries with modified Hammett constants reveal a mechanistic picture of the epoxidation reaction, supporting previou...