Catenated Compounds – Group 17 – Polyhalides

Halogen bonding between metal-bound I3− and unbound I2: the trapped I2⋯I3− intermediate in the controlled assembly of copper(i)-based polyiodides

“…Polyhalides are a subject of intensive studies, 1–3 in view of their broad application as, for instance, electrolytes for batteries and dye sensitized solar cells, 1,2 mildly selective oxidants for organic synthesis, 2 and synthons for the construction of metal–organic frameworks. 4 In particular, polyhalides (especially polyiodides) of various transition metals are utilized for the design of coordination networks 4 and fabrication of semiconductive materials; 5 halogen–halogen closed-shell bonding interactions have been widely studied theoretically.…”

On the non-existence of a square-planar pentaiodide coordination complex I(i)4−

“…Polyhalide compounds in general and polyiodides in particular offer a rich structural chemistry of catenated, low-dimensional compounds. 1,2 The vast majority of polyiodide compounds can be visualized in terms of simple coordination chemistry, in which the ionic building blocks of I − and I 3 − can be regarded as solvated by the neutral solvent molecules I 2 . The sticky bonding properties of the relatively small and few building blocks generate chain-like structures, which can be attributed to topological electron densities of the building blocks (σ-holes).…”

“…The sticky bonding properties of the relatively small and few building blocks generate chain-like structures, which can be attributed to topological electron densities of the building blocks (σ-holes). 2,3 The predominant bonding contributions have been assigned to secondary interactions, such as dispersion and induction, complemented by weak covalency mediated by overlap of the large valence orbitals of iodine. 4 However, this scheme has recently been challenged and the bonding been solely attributed to non-covalent interactions.…”

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

“…[16] Intensive Untersuchungen der Polyiodide brachten seither eine Vielzahl an Mono-, Di-, Tr i-und sogar Te traanionen hervor,d eren Chemie und Struktur in umfangreichen Übersichtsartikeln zusammengefasst wurden. [17,18] Aufd en ersten Blick scheint es,a ls müsste die Zahl der Polyhalogenide innerhalb der Gruppe 17 von den leichteren zu den schwereren Halogenen zunehmen. Tatsächlich gilt dieser Tr end nur vom Fluor zum Iod und bricht abrupt zwischen Iod und Astat ab.D ieser Umstand erklärt sich aus dem reichen Vorkommen von Fluor, Chlor,B rom und Iod, im Unterschied zu Astat, von dem ausschließlich radioaktive Isotope bekannt sind, die sich nur in sehr geringen Mengen mit Te ilchenbeschleunigern erzeugen lassen.…”

“…In der Vergangenheit wurden einige Übersichtsartikel zu Polyhalogen-Anionen publiziert, die sich nach den Elementen ordnen lassen:a llgemeine Artikel zu Polyhalogeniden [22,23] und Polyiodiden [17,18] sowie sehr ausführliche Artikel zu Polyfluoriden, [24] -chloriden [25] und -bromiden. [26] Adonin et al verçffentlichten zudem kürzlich eine Arbeit zu Polyhalogenid-gebundenen Metallkomplexen.…”