| Summary: | A large number of metallaborane clusters and their derivatives with various structural arrangements are known. Among them, M<sub>2</sub>B<sub>5</sub> clusters and derivatives constitute a significant class. Transition metals present in these species span from group 4 to group 7. Their structure can vary from oblatonido, oblatoarachno, to arachno type open structures. Many of these clusters appear to be hypoelectronic and are often considered as ‘rule breakers’ with respect to the classical Wade–Mingos electron counting rules. This is due to their unique highly oblate (flattened) deltahedral structures featuring a cross-cluster M−M interaction. Many theoretical calculations were performed to elucidate their electronic structure and chemical bonding properties. In this review, the synthesis, structure, and electronic aspects of the transition metal M<sub>2</sub>B<sub>5</sub> clusters known in the literature are discussed. The chosen examples illustrate how, in synergy with experiments, computational results can provide additional valuable information to better understand the electronic properties and electronic requirements which govern their architecture and thermodynamic stability.
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