Stereochemical aspects of phosphor-1,1-dithiolato metal complexes: Coordination patterns, molecular structures and supramolecular associations in dithiophosphinates and related compounds

Mono urotropine adducts of some binary zinc xanthates and dithiocarbamates: solid-state molecular structures and supramolecular self-assembly

“…Compared to the literature molecules, the second dithiocarbamate and hmta ligands are pushed away from the symmetric dithiocarbamate ligand, again due to the close approach of a symmetry related hmta molecule to enable the C-H By contrast to xanthate and dithiocarbamate ligands, equivalent canonical structures to those shown in Figure 10 do not exist for the dithiophosphate, − [S 2 P(OR) 2 ], and dithiophosphinateand, − S 2 PR 2 , ligands owing to the tetrahedral geometry of the phosphorus atom. Accordingly, these ligands are less likely to be chelating and show a greater propensity for bridging metal centres [7,8,47,48], often via secondary interactions [49,50], and therefore, to form coordination polymers with polyfunctional Lewis base donors [51,52]. In this context, all of the known metal dithiophosphates/dithiophosphinates adducts of hmta bar one, have the latter coordinating in a bidentate, bridging mode [53][54][55].…”

Supramolecular association in (μ2-pyrazine)-tetrakis(N,N-bis(2-hydroxyethyl)dithiocarbamato)dizinc(II) and its di-dioxane solvate

“…The structural chemistry of metal dithiocarbamates ( − S 2 CNRR′), both transition metal [1] and main group element [2], is well studied and is rich and diverse, certainly compared with related metal xanthates ( − S 2 COR) [3] and metal dithiophosphates [ − S 2 P(OR) 2 ] [4]; R,R′ = alkyl, aryl. In terms of supramolecular chemistry, owing to the presence of peripheral alkyl/aryl groups of the − S 2 CNRR′ anions, which are not capable of forming significant intermolecular interactions such as hydrogen bonding, their self-assembly is usually limited to secondary interactions [5,6], occurring between the metal centre and sulfur atoms derived from neighbouring molecules and, from a crystal engineering perspective, steric effects are paramount in this regard [7].…”

Serendipitous compositional and structural diversity in urotropine adducts of binary cadmium xanthates

“…1 [1][2][3][4][5][6][7]. Being easy to prepare and having a great propensity for complexing heavy elements ranging from the transition metals, lanthanides, and relevant to the present study, main group elements, it is not surprising that there is an enormous wealth of structural data for metal 1,1-dithiolates [1][2][3][4][5][6][7]. Amongst these, the structural chemistry exhibited by the binary cadmium xanthates, Cd(S2COR)2 is remarkable for its diversity and complexity [1].…”