Photochemical water splitting mediated by a C1 shuttle.

The possibility of performing photochemical water splitting in a two-stage system, separately releasing the H2 and O2 components, has been probed with two separate catalysts and in combination with a formaldehyde/formate shuttling redox couple. In the first stage, formaldehyde releases hydrogen vigorously in the presence of an Na4[Fe(CN)6]·10H2O catalyst, selectively affording the formate anion. In the second stage, the formate anion is hydro-genated back to formaldehyde by water and in the presence of a Bi2WO6 photocatalyst whilst releasing oxygen. Both stages operate at room temperature and under visible light irradiation. The two separate photocatalysts are compatible since water splitting can also be obtained in one-pot experiments with simultaneous H2/O2 evolution.

Reactivity of calix-tetrapyrrole SmII and SmIII complexes with acetylene: isolation of an "N-confused" calix-tetrapyrrole ring.

The nature of the substituents present on the calix-tetrapyrrole tetra-anion ligand [[R2C(C4H2N)]4]4- (R = [-(CH2)5-]0.5, Et) determines the type of reactivity of the corresponding SmII compounds with acetylene. With R = [-(CH2)5-]0.5, dehydrogenation occurred to yield the nearly colorless dinuclear diacetylide complex [[[[-(CH2)5-]4-calix-tetrapyrrole]SmIII]2(mu-C2Li4)].THF as the only detectable reaction product. Conversely, with R = Et, acetylene coupling in addition to dehydrogenation resulted in the formation of a dimeric butatrienediyl enolate derivative [[(Et8-calix-tetrapyrrole)SmIII[Li[Li(thf)]2(mu-OCH=CH2)]]2(mu,eta2,eta'2-HC=C=C=CH)]. Reaction of the trivalent hydride [(Et8-calix-tetrapyrrole)(thf)SmIII[(mu-H)[Li(thf)]]2 or of the terminally bonded methyl derivative [(Et8-calix-tetrapyrrole)(CH3)SmIII[[Li(thf)]2[Li(thf)2](mu3-Cl)]] with acetylene resulted in a mixture of the carbide [[(Et8-calix-tetrapyrrole)SmIII]2(mu-C2Li4)].Et2O with the dimerization product [[(Et8-calix-tetrapyrrole)SmIII[Li[Li(thf)]2(mu3-OCH=CH2)]]2-mu,eta2,eta'2-HC=C=C=CH)]. The same reaction also yielded a third product, a trivalent complex [[(Et8-calix-tetrapyrrole)SmIII[Li(thf)2]]2], in which the macrocycle was isomerized by shifting the ring attachment of one of the four pyrrole rings.

Tetrametallic Reduction of Dinitrogen: Formation of a Tetranuclear Samarium Dinitrogen Complex.

The cooperative attack of four (dipyrromethanyl)Sm(II) units on dinitrogen resulted in a novel tetranuclear samarium dinitrogen complex (shown schematically). The presence of halogen atoms inhibited reactivity with dinitrogen through the assembly of divalent samarium clusters. dipyrr=diphenylmethyldipyrrolide dianion.

A Paramagnetic Diniobium Complex with a Very Short Nb-Nb Distance: Evidence for a Pseudo Nb-Nb Triple Bond?

In spite of the short Nb-Nb distance (2.268 Å) and the presumable existence of an Nb identical withNb bond, the paddle-wheel-shaped diniobium(II) complex 1 is paramagnetic. Theoretical calculations indicate that the presence of LiCl moieties on the intermetallic axis lowers the Nb-Nb bond order and is responsible for the observed paramagnetism.