The conversion of CO₂ into multicarbon (C₂₊) compounds by reductive homocoupling offers the possibility to transform renewable energy into chemical energy carriers and thereby create “carbon‐neutral” fuels or other valuable products. Most available studies have employed heterogeneous metallic catalysts, but the use of molecular catalysts is still underexplored. However, several studies have already demonstrated the great potential of the molecular approach, namely, the possibility to gain a deep mechanistic understanding and a more precise control of the product selectivity. This Minireview summarizes recent progress in both the thermo‐ and electrochemical reductive homocoupling of CO₂ toward C₂₊ products mediated by molecular catalysts. In addition, reductive CO homocoupling is discussed as a model for the further conversion of intermediates obtained from CO₂ reduction, which may serve as a source of inspiration for developing novel molecular catalysts in the future.

Chemoselective semihydrogenation of alkynes to alkenes with E- or Z-stereoselectivity is among the most important transformations in the synthesis of highly functional organic building blocks. Use of hydrogen transfer reagents instead of gaseous hydrogen represents a viable, safe alternative in many cases. This review summarises recent developments in the field using homogeneous, molecularly defined catalyst systems with focus on hydrogen sources and mechanistic aspects of the respective systems.

This perspective gives an overview of recent developments in the chemistry of heterometallacycles of group 4 metallocenes. This class of compounds has been known for several decades now, however, in recent years significant efforts were made in order to further explore the structural scope of these complexes and their potential in catalytic applications. This overview shows some special heterometallacycles which could be of great interest for theoretical and synthetic chemists, owing to their unusual structural and bonding parameters as well as their applicability in a wide range of synthetic and catalytic transformations.

The complex [(PNHP)Fe(H)(CO)(HBH₃)] (PNHP = HN(CH₂CH₂Pi-Pr₂)₂) serves as a catalyst precursor for the selective dehydrocoupling of methylamine borane at room temperature, tentativelyviaan off-metal polymerisation pathway.

Phospha–Wittig reagents of the type RPPMe₃ can be considered as phosphine-stabilized phosphinidenes and were shown to react with NHCs and NHOs to afford NHC phosphinidene adducts or P-substituted NHOs, respectively.