1,1-Ethylenedithiolato Complexes of Palladium(II) and Platinum(II) with Isocyanide and Carbene Ligands

Abstract

The reactions of [Tl(2)[S(2)C=C[C(O)Me](2)]](n) with [MCl(2)(NCPh)(2)] and CNR (1:1:2) give complexes [M[eta(2)-S(2)C=C[C(O)Me](2)](CNR)(2)] [R = (t)Bu, M = Pd (1a), Pt (1b); R = C(6)H(3)Me(2)-2,6 (Xy), M = Pd (2a), Pt (2b)]. Compound 1b reacts with AgClO(4) (1:1) to give [[Pt(CN(t)Bu)(2)](2)Ag(2)[mu(2),eta(2)-(S,S')-[S(2)C=C[C(O)Me](2)](2)]](ClO(4))(2) (3). The reactions of 1 or 2 with diethylamine give mixed isocyanide carbene complexes [M[eta(2)-S(2)C=C[C(O)Me](2)](CNR)[C(NEt(2))(NHR)]] [R = (t)Bu, M = Pd (4a), Pt (4b); R = Xy, M = Pd (5a), Pt (5b)] regardless of the molar ratio of the reagents. The same complexes react with an excess of ammonia to give [M[eta(2)-(S,S')-S(2)C=C[C(O)Me](2)](CN(t)Bu)[C(NH(2))(NH(t)Bu)]] [M = Pd (6a), Pt (6b)] or [M[eta(2)-(S,S')-S(2)C=C[C(O)Me](2)][C(NH(2))(NHXy)](2)] [M = Pd (7a), Pt (7b)] probably depending on steric factors. The crystal structures of 2b, 4a, and 4b have been determined. Compounds 4a and 4b are isostructural. They all display distorted square planar metal environments and chelating planar E,Z-2,2-diacetyl-1,1-ethylenedithiolato ligands that coordinate through the sulfur atoms.

Formation of an Iron(II) Carbene–Thiolato Complex by Insertion of Carbon Monoxide into an SiC Bond

“…Hence, complexes A bearing both Fischer carbene and thiolato ligands would be in equilibrium with the thiametalacyclopropane form B 1. Although the existence of an equilibrium between A and B was supported by NMR spectroscopy and reactivity studies,1a such complexes are scarce 2–4. A possible reason for this paucity lies in facile intramolecular nucleophilic substitution to form the RS‐substituted carbene complex C…”

Synthesis of stannic(IV) complexes: Their structural elucidation in solid and solution state and antimicrobial activity

“…1,1-Dithiolate ligands have recently attracted much attention mainly because of their interesting photophysical properties derived from their extensive electron delocalization onto all of the ligand atoms [2]. Indeed, the increasing renewed interest nowadays to these species is due to their high stability, solvatochromic behavior, room temperature luminescence in solution [3], and their status as excellent candidates for applications such as photocatalysis [4].…”

Synthesis and characterization of a complex salt and heterobimetallic coordination polymers of 1-benzoyl-1-cyanoethylene-2,2-dithiolate

“…Metal complexes with bifunctional unsaturated sulfur-containing ligands are of great importance from the viewpoint of their magnetic and electrical conducting behaviour. Planar bis-1,2-dithiolene complexes, [M(1,2-dithiolene) 2 ] n) [M ¼ Ni, Pd, Pt or Cu; dithiolene ¼ 1,3-dithiole-2-thione-4,5-dithiolate (dmit 2) ) or maleonitriledithiolate (mnt 2) ); n ¼ )1, )2] are well known electron acceptors and have been widely utilized for the synthesis of monometallic and bimetallic chargetransfer salts as well as metalloligands for the preparation of bridged heterobimetallic complexes with unusual magnetic and electrical properties [5][6][7][8][9][10][11][12][13].…”

“…Although 1,2-dithiolene metal complexes have been much more intensively studied than those with 1,1-dithioligands such as isomaleonitriledithiolate (1-mnt 2) ), 2-ethoxycarbonyl-2-cyanoethylene-1,1-dithiolate (ecda 2) ) and 1,1-ethylenedithiolate ligands [5][6][7][8][9][10][11][12][13], 1,1-dithio ligands have recently attracted attention because of (i) greater electron delocalization beyond the MS 2 bonds, i.e. through CAS, C@C and CACN bonds [14], and (ii) their interesting photophysical properties and potential applications in new inorganic complex based electrical conductors [9][10][11][12][13].…”

“…through CAS, C@C and CACN bonds [14], and (ii) their interesting photophysical properties and potential applications in new inorganic complex based electrical conductors [9][10][11][12][13]. As compared to the complexes of i-mnt 2) and ecda 2) ligands, those with 1-benzoyl-1-cyanoethylene-2,2-dithiolate (bcd 2) ) are very scarce [15].…”