Electronic laboratory notebook: the academic point of view.

Based on a requirement analysis and alternative design considerations, a platform-independent electronic laboratory notebook (ELN) has been developed that specifically targets academic users. Its intuitive design and numerous productivity features motivate chemical researchers and students to record their data electronically. The data are stored in a highly structured form that offers substantial benefits over laboratory notebooks written on paper with regard to data retrieval, data mining, and exchange of results.

A new synthesis of charge-neutral tris-pyrazolyl and -methimazolyl borate ligands.

The dimethylamine in the adducts [(HNMe(2))B(azolyl)(3)] (azolyl=methimazolyl, pyrazolyl), obtained by reaction of the azole with B(NMe(2))(3), can readily be substituted with a range of nitrogen donors to provide new charge-neutral, tripodal ligands in high yield. This observation has led to a revision of an earlier interpretation of the mechanism of the formation of these species. The donor properties of the ligands [(nmi)B(azolyl)(3)] (nmi=N-methylimidazole) have been compared with their anionic analogues [HB(azolyl)(3)](-) by synthesis of their manganese(I)-tricarbonyl complexes and comparison of their infrared nu(CO) energies. This comparison indicates that the new neutral ligands are only marginally weaker donors than the corresponding anionic hydrotris(azolyl)borate ligands. This may be explained by the ability of the attached nmi ring to stabilize a positive charge remotely from the coordinated metal, which may also account for the fact that the [(nmi)B(pyrazolyl)(3)] ligand is a substantially stronger donor than the similarly neutral tris(pyrazolyl)methane ligand.

Tripodal borate ligands from tris(dimethylamino)borane: the first synthesis of a chiral tris(methimazolyl)borate ligand, and the crystal structure of a single diastereomer pseudo-C3-symmetric Ru(II) complex.

The activation of tris(dimethylamino)borane towards reaction with a chiral methimazole by N-methylimidazole has been used to prepare the first example of a chiral tris(methimazolyl)borate ligand. Coordination of this neutral ligand to Ru(II) has been achieved by reaction with [(p-cymene)RuCl(2)](2) to provide a single diastereomer complex in which the chirality of the methimazolyl substituents dictate the chirality of the bicyclo[3.3.3]cage formed by the ligand on coordination to the metal. The alternative approach to chiral tris(methimazolyl)borate ligands involving the introduction of a chiral group onto the boron atom has been explored by replacing N-methylimidazole in the above reaction by chiral oxazolines as activating bases in reaction with simple methimazole. However, although the B(NMe(2))(3) is activated to reaction with methimazole by these oxazolines, an intramolecular oxazoline ring-opening by a coordinated methimazolyl sulfur occurs and prevents the successful synthesis of these ligands.

Reaction of azole heterocycles with tris(dimethylamino)borane, a new method for the construction of tripodal borate-centred ligands.

Reaction of 2-mercapto-1-methylimidazole (methimazole) with tris(dimethylamino)borane, B(NMe2)3, provides the tetrahedral dimethylamine adduct of tris(methimazolyl)borane, [(Me2HN)B(methimazolyl)3]. By contrast, imidazole, 2-methylimidazole, 2-chloroimidazole and benzimidazole provide the homoleptic tetra-azolyl systems H[B(azolyl)4], and the same product is obtained even when a substoichiometric quantity of the heterocyle is employed. The change in reaction outcome is correlated with the variation of basic pKa for the heterocycles. A simple acid-base reaction with elimination of HNMe2 is proposed for the reaction with the weakly basic, but more strongly acidic, methimazole. However, for the more strongly basic imidazoles, initial coordination of the heterocycle imine nitrogen to the weakly Lewis acidic boron centre in B(NMe2)3 to form the tetrahedral adduct [(azole)B(NMe2)3] is proposed. The greater availability of the NMe2 lone pairs in this species results in increased basicity and a rapid reaction with further heterocycle to provide the observed H[B(azolyl)4] products. For 2-nitroimidazole, the low basicity (and increased N-H acidity) results in the formation of [(HNMe2)B(2-nitroimidazolyl)3] on reaction with B(NMe2)3, analogous to the product formed with methimazole. Both [(HNMe2)B(methimazolyl)3] and H[B(benzimidazolyl)4] have been structurally characterised by single crystal X-ray crystallography. This chemistry has been exploited to provide a new synthesis of borate-centred tripod ligands, whereby N-methylimidazole is used to activate B(NMe2)3 to reaction with methimazole to form the new ligand [(N-methylimidazole)B(methimazolyl)3] in good yield and a complex of this ligand with Ru(II) has been structurally characterised.