Molecular and supramolecular chemistry of mono- and di-selenium analogues of metal dithiocarbamates

Abstract

This bibliographic review summarises the coordination chemistry of mono-and diselenium analogues of metal dithiocarbamate ligands, [RRꞌNCS2]-, as revealed by X-ray crystallography and spectroscopy (77 Se NMR and infrared). The Se-ligands are usually chelating but, bridging modes, up to 4, are known. Reflecting the larger size, greater polarisability and presence of a polar-cap (-hole), selenium atoms are more likely to be 2 involved in secondary-bonding (chalcogen-bonding) than sulphur when a competition exists. Isostructural relationships are established across the series in about one-third of the structures.

Zero-, one-, two- and three-dimensional supramolecular architectures sustained by Se…O chalcogen bonding: A crystallographic survey

“…It was in the context of a long-held interest in secondary bonding interactions and the supramolecular architectures they sustain [56] , [57] , [58] , [59] , [60] , [61] , [62] , [63] , [64] and in the aforementioned biological relevance of Se … O chalcogen bonding interactions that the present survey of Se … O interactions operating in crystals was undertaken. This review of the crystallographic literature serves to highlight the diverse nature of selenium atom environments, geometries, oxidation states and numbers and types of Se … O secondary bonding interactions formed by selenium and the wide variety of supramolecular architectures these chalcogen bonding interactions sustain.…”

A Survey of Supramolecular Aggregation Based on Main Group Element⋯Selenium Secondary Bonding Interactions—A Survey of the Crystallographic Literature

“…This falls off to 16% for bismuth to 10% for tellurium and then 6% (arsenic) and 5% (tin and antimony). One reason for the low adoption rates relates to the observation that secondary bonding interactions are extremely sensitive to steric hindrance-bulky groups present on the organometal center and/or ligands bound to the metal can preclude the formation of secondary bonding interactions [15][16][17][18][19][20][21][22][23]; steric considerations have been exploited for the rational design of coordination polymers in zinc and cadmium dithiolate chemistry [74]. However, in a recent commentary on supramolecular association involving metal centers, it was concluded that the energies of stabilization provided by various secondary bonding interactions was in the same range and often exceeded the energy of stabilization provided by conventional hydrogen bonding interactions [77].…”

Supramolecular aggregation patterns featuring Se⋯N secondary-bonding interactions in mono-nuclear selenium compounds: A comparison with their congeners

“…In continuation of a long-held interest of the supramolecular association in crystals mediated by secondary-bonding and related interactions involving the main group elements [37][38][39][40][41][42][43][44][45][46][47][48][49][50][51], the present survey focuses upon the delineation of the supramolecular architectures featuring Se … N interactions in the crystals of mononuclear selenium molecules which operate in the absence of other obvious supramolecular synthons, such as hydrogen-bonding. This survey reveals a full range of zero-, one-, two-and three-dimensional architectures featuring Se … N interactions.…”