The dithiolene ligand and tetrathiafulvalene precursor molecules 4,5-bis(bromomethyl)-1,3-dithiol-2-one and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one

Abstract

The crystal structures of 4,5-bis(bromomethyl)-1,3-dithiol-2-one, C(5)H(4)Br(2)OS(2), (I), and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one, C(5)H(8)O(7)P(2)S(2), (II), occur with similar unit cells in the same monoclinic space group. Both molecules reside on a twofold symmetry axis coincident with the C=O bond, so that the substituents in the 4- and 5-positions project above and below the plane of the 1,3-dithiol-2-one ring. In both structures, the molecules align themselves in a head-to-tail fashion along the b axis, and these rows of molecules then stack, with alternating directionality, along the c axis. For (II), an extensive network of intermolecular hydrogen bonds occurs between molecules within the same stack and between adjacent stacks. Each -CH(2)P(O)(OH)(2) group participates in four hydrogen bonds, twice as donor and twice as acceptor.

A Structural and Spectroscopic Investigation of Octahedral Platinum Bis(dithiolene)phosphine Complexes: Platinum Dithiolene Internal Redox Chemistry Induced by Phosphine Association

“…Compound 2 is a convenient protected form of the dithiolene ligand that is readily unmasked via base hydrolysis and then coordinated to the desired transition complex, usually by the displacement of halide ligands. Bond lengths and angles for 2 (Table S2 in the SI) are similar to those reported for related compounds that have been characterized structurally. ,− One of the types of metal complexes readily formed from an in situ generated ene-1,2-dithiolate is a dialkyltin dithiolene compound, such as 3 (Scheme and Figure ). Two independent molecules of 3 occur in the asymmetric unit of the cell, one of which is presented in Figure , and form relatively close nonbonding intermolecular Sn···S contacts via an offset head-to-head packing arrangement (Figure S17 in the SI).…”

6,6-Dimethyl-2H,5H,6H,7H-1,3-dithiolo[4,5-f][1,5,3]dithiasilepin-2-one

“…For the synthesis, see: Li et al (2012). For related structures, see: Arumugam et al (2011);Hou et al (2009 Table 1 Hydrogen-bond geometry (Å , ).…”