Synthesis, cyclic voltammetry and 31P {H} NMR spectra of [M3E2L3]2+ clusters; M=Ni, Pd or Pt; E=S, Se or Te; L=bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or 1,4-bis(diphenylphosphino)butane

Reactivity of dipyrimidyldiselenides with [M(PPh3)4] and 2-pyrimidylchalcogenolates with [MCl2(diphosphine)] (M = Pd or Pt)

“…The 31 P NMR chemical shifts for 7 are in accordance with BPh 4 /PF 6 salts of [Pd 3 (m-E) 2 (P X P) 3 ] 2þ cations reported earlier [39,43,44]. These complexes have been isolated in low yields by a reaction between [PdCl 2 (P X P)] and NaEH (E ¼ Se or Te) in the presence of NaBPh 4 or NaPF 6 [39,43]. The selenidobridged complexes have been isolated in fairly good yield through unprecedented cleavage of CeSe bond of selenocarboxylate during the reaction of [Pd(SeCOAr) 2 (P X P)] with [PdCl 2 (P X P)] in the presence of NaBPh 4 in CH 2 Cl 2 eMeOH solvent mixture [44].…”

“…When the mononuclear complexes 4a and 5e were left in halogenated solvents (CDCl 3 or CH 2 Cl 2 ) for several hours, crystals of 6 were isolated. The 31 P NMR chemical shifts and 1 J(PteP) values for 6 are in conformity with the reported values [39,40]. The formation of telluride-bridged complex 6 either from 5e in CDCl 3 or in the reaction between PtCl 2 (dppe) and NaTeC 4 H 3 N 2 takes place via a facile TeeC bond cleavage.…”

“…The 1 H NMR spectra were devoid of any EC 4 H(4,6-R 2 )N 2 proton resonances as expected. The 31 P NMR chemical shifts for 7 are in accordance with BPh 4 /PF 6 salts of [Pd 3 (m-E) 2 (P X P) 3 ] 2þ cations reported earlier [39,43,44]. These complexes have been isolated in low yields by a reaction between [PdCl 2 (P X P)] and NaEH (E ¼ Se or Te) in the presence of NaBPh 4 or NaPF 6 [39,43].…”

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

“…Thus, electrochemical studies on the trimetallic clusters [{L 2 Pt(µ 3 -S) 2 PtL 2 }PtL 2 ] 2ϩ (L 2 ϭ dppm, dppe, dppp, dppb) have shown that the cationic core {Pt 3 (µ 3 -S) 2 } 2ϩ is able to accept one electron, as observed by means of cyclic voltammetric measurements. [40] These data indicate that the electron-donor properties of the {Pt(µ-S) 2 Pt} core can be reversed, thus becoming an electron-acceptor, after coordination to a metal center. The electrochemical features of this family of trimetallic complexes are also highly dependent on the chelate ring size of the phosphane ligands.…”

Emerging trends in organotellurolate chemistry derived from platinoids

“…Similarly, various trinuclear products have been isolated by the reaction between M 2+ , PXP, and NaTeH in N,Ndimethylformamide for more than 20 h stirring (Scheme 22). 143 Undoubtedly, strong coordinating solvents, like DMF, CH 3 CN, may enable the coordination of tellurium to further platinum moieties with ease, resulting in tri-to pentanuclear products. [143][144][145][146] Morley et al also isolated the trinuclear product [Pt 3 {(m-Te) 2 (dppe) 2 } 2 ] 2+ by the oxidative addition of [Pt(dppe) 2 ] and vitreous tellurium under reuxing for 5 h. 147 The isolation of the trinuclear product via an oxidative addition mode is unprecedented and could be rationalized by the fact that the higher nucleophilicity of tellurium makes it highly susceptible to the nucleophilic attack of chlorinated solvents.…”