The mechanism of Fe-catalyzed cyclic carbonate formation of CO ₂ and internal epoxides was studied to identify design strategies for more efficient catalysts.

The artificial nucleobases 6-(2′-thienyl)-purine (6TP) and 6-(2′-furyl)-purine (6FP) have been investigated in terms of their applicability in metal-mediated base pairs. In principle, these nucleobases should be capable of providing an S,N- and O,N-coordination environment, respectively. Two metal complexes have been synthesized and structurally characterized, using the N9-methylated derivatives of 6TP and 6FP as model nucleobases. The silver(I) complex [Ag(9-Me6TP)(CH₃CN)(NO₃)]_n is of polymeric nature. The thienyl substituent is not involved in metal binding. In contrast, the dinuclear copper(II) complex [Cu(9-Me6FP)Cl₂(OH₂)]₂ clearly shows that the furyl substituent can participate in the coordination of the metal ion. Oligonucleotide double helices comprising a 6TP:6TP or a 6FP:6FP mispair are slightly stabilized in the presence of silver(I). However, a distinction between the formation of a metal-mediated base pair and an unspecific binding event cannot be finally made. Based on these studies, it is proposed that the formation of Hoogsteen-type metal-mediated base pairs should be the more promising alternative compared with the originally anticipated Watson–Crick-type metal-mediated base pairs.

A paramagnetic cobalt–SiH intermediate possessing the Co–(η ¹ -H–Si) moiety shows unusual Si–H bond activation studied by ENDOR, XRD and DFT.