The reactions of [M(dppe)2] (M=Pd, Pt) with elemental selenium or tellurium: preparation and structure of the platinum polyselenide [PtSe4(dppe)]

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

“…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 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]. In an alternative route 7a has been prepared in 52% yield by Morley et al by the reaction of [Pd(dppe) 2 ] with selenium powder in CH 2 Cl 2 [40].…”

The First Disulfur and Diselenium Complexes of Platinum: Syntheses and Crystal Structures

“…These differences in the bond lengths correlate well with the approximately 0.13 Å larger covalent radius of selenium than that of sulfur 24. It is noteworthy that the P1‐Pt1‐P2 bond angles are somewhat larger than those for other related platinum polychalcogenido complexes, for example [(dppe)PtS 4 ] 86.8(1)°,23 [(Ph 3 P) 2 PtS 4 ] 99.3(2)°,7b [(Ph 3 P) 2 Pt(S 3 O)] 98.47(8)°,25 [Pt 2 ( μ ‐S) 2 (dppy) 4 ] 102.98(6)° (dppy=2‐diphenylphosphinopyridine),26 [(dppe)PtSe 4 ] 86.31(20)°,8a [Pt 2 ( μ ‐Se) 2 (PPh 3 ) 4 ] 99.6(1)°,27 and an analogous dioxygen complex, [(Ph 3 P) 2 PtO 2 ] 100–101°,9 which reflects the severe steric repulsion between two Bbt groups. We assume that these larger P1‐Pt1‐P2 angles of 4 b and 5 b contribute to the stabilization of the three‐membered PtE 2 ring systems 28…”

Reaction of the Tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) with Activated Alkynes to Form Dithiolenes and Diselenolenes

“…[13,14] We now report the preparation of a number of dithiolenes and diselenolenes starting from the tetrachalcogenides [PdS 4 (dppe)], [PtS 4 (dppe)], and [PtSe 4 (dppe)] [15] [dppe ϭ 1,2-bis(diphenylphosphanyl)ethane].…”