Desulphurisation–dimerisation of dithioacetals with W(CO)₆

Abstract

Dithioacetals undergo desulphurisation-dimerisation to give the corresponding dimeric alkenes in good to excellent yields on treatment with W(CO)6.

Extending The Reaction Landscape of the {Pt(μ‐S)2Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

“…On the basis of these general rules it is clear that complexes with the formula [(phosphane)Pt(µ-S) 2 Pt(phosphane)] are very well suited to adopt bent structures. However, steric interactions between terminal ligands can prevent the folding of the {M 2 S 2 } core, as observed for M ϭ Pt and L ϭ PPh 2 py [14] or PPh 3 , [16] where the resulting core is planar or almost planar, respectively. Moreover, the increase in the PtϪX distances from X ϭ S to Te could account for the planar structures observed for the {Pt(µ-X) 2 Pt} core with Se (Table 2).…”

“…[13] Other less direct routes entail the oxidation of [PtL 4 ] with S 8 , which affords phosphane sulfide as secondary product, [7] or, the reaction between [PtCl 2 L 2 ] and NaSH. [14] The latter involves the formation of [Pt(SH) 2 L 2 ] first and then its subsequent reaction with a second equivalent of [PtCl 2 L 2 ], thus yielding [L 2 Pt(µ-S) 2 PtL 2 ] plus two equivalents of HCl. However, as commented below, the presence of HCl is inconvenient as it can cause disintegration of the {Pt(µ-S) 2 Pt} core.…”

“To Bend or not To Bend?” Both! The Planar and Bent Structures of[(Ph3P)4Rh2(μ‐F)2]

“…[5] The Pt 2 (µ-S) 2 moiety in complexes of the type [L 4 Pt 2 (µ-S) 2 ] is commonly bent, [1] though for L = 2-(diphenylphosphanyl)pyridine, a planar structure was reported. [6] Depending on the nature of the counterion X in [Pt 2 (NH 3 ) 4 (µ-OH) 2 ]X 2 , both the planar (X = NO 3 [7] or 1/2CO 3 , dihydrate [8] ) and bent (X = ClO 4 [9] ) forms of the cation can exist in the crystalline state. The 3340 studies point to weak C-H···F intramolecular bonding as an additional factor affecting the choice between the planar and bent geometries.…”

“…[1] The energy cost of bending for such complexes is normally low, often only a few kcal mol -1 , [1,4] suggesting that both forms could be found experimentally for a single species. Both almost planar and more bent molecules have been found in the crystal structure of nonsquare-planar [Co 2 (µ-PPh 2 ) 2 (CO) 6 ]. [5] The Pt 2 (µ-S) 2 moiety in complexes of the type [L 4 Pt 2 (µ-S) 2 ] is commonly bent, [1] though for L = 2-(diphenylphosphanyl)pyridine, a planar structure was reported.…”

Edge-Sharing Binuclear d8 Complexes with XR Bridges: Theoretical and Structural Database Study of their Molecular Conformation

“…[2,3] Other interesting properties of these compounds include their catalytic activity, [2, 4±6] luminescent behavior, [7] or their potential use as therapeutic agents for cisplatin nephrotoxicity. [8] Despite the large amount of available structural data, a full understanding of the factors that determine the molecular structure of a particular compound has not been achieved.…”