Reactivity of Dipyridyl Ditellurides with (Diphosphine)Pt⁰and 2-Pyridyltellurolates with (Diphosphine)PtCl₂and Isolation of Different Structural Motifs of Platinum(II) Complexes

Abstract

Oxidative addition reaction of dipyridyl ditellurides to [Pt2(dppm)3] gave two types of complexes, [Pt­{2-Te-C5H3(3-R)­N}2(dppm)] (1) and [Pt­{PPh2C­(TeC5H3(3-R)­N)2PPh2}2] (2) (R = H or Me), in ∼65 and ∼20% yield, respectively. Both these complexes are also formed in the substitution reaction between [PtCl2(dppm)] and NaTeC5H3(3-R)­N. Treatment of [Pt­(dppe)2] with dipyridyl ditellurides yielded an oxidative addition product, [Pt­{2-Te-C5H3(3-R)­N}2 (dppe)] (3) (R = H or Me), exclusively. In a substitution reaction of [PtCl2(dppe)] with NaTeC5H3(3-Me)­N a complex of composition Pt­{TeC5H3(3-Me)­N}­(dppe)­Cl (4) was formed. The reaction between either [Pt­(dppp)2] and Te2(C5H3(3-Me)­N)2 or [PtCl2(dppp)] and NaTeC5H3(3-R)N afforded a mixture of [Pt­{2-Te-C5H3(3-Me)­N}2(dppp)] (5) and [Pt3Te2(dppp)3]2+ (6), which were separated by column chromatography. All the complexes were characterized by elemental analyses and NMR (1H, 31P, 195Pt) spectroscopy. The molecular structures of [Pt­{PPh2C­(TeC5H4N)2PPh2}2] and [Pt2{TeC5H3(3-Me)­N}2(dppe)2]­[BPh4]2 were established by single-crystal X-ray diffraction analyses. The bonding, charge transfer, and geometry of compounds [Pt­{2-Te-C5H3(3-R)­N}2(dppm)] (1), [Pt­{PPh2C­(TeC5H3(3-R)­N)2PPh2}2] (2), and [Pt3Te2(dppp)3]2+ (6) have been analyzed through relativistic density functional calculations.

Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

“…The 31 P NMR spectrum of complex 2b, 2c, 2d exhibited two 31 P resonance at δ ~ -7 ppm and -11 ppm with different 1 J(Pt-P) coupling constants. The former resonance is deshielded compared to latter one, with 195 Pt-31 P coupling of ~ 2850 Hz indicative of selenolate ligand trans to the phosphine ligand [33][34][35].…”

“…The Hz)] [37][38]. Apparently, during the longer acquisition 195 Pt NMR spectrum of 2d also displayed a triplet at δ = -4700 ppm [ 1 J(Pt-P) = 2718 Hz] as well, indicating coordination of two equivalent phosphorus nuclei [39]. The appearence of new resoance suggests the slowly disintigration of compound in CDCl3 solution to give an unknown moiety.…”

Oxidative addition reactions of nicotinamide based organoselenium compounds on [M(PPh3)4] (M=Pd or Pt): An insight study for the formation of several isolable products

“…complexes are stable in halogenated solvents for several days, the corresponding SeC 5 H 3 (3-R)N derivatives tend to dissociated to give Se X N chelated products [19,20]. In contrast, the pyrimidylselenolate complexes, in addition to Se X N chelation, also undergo SeeC bond cleavage [17].…”

Electrochemiluminescence Detection of TNT by Resonance Energy Transfer through the Formation of a TNT–Amine Complex

“…The strategies adopted for the synthesis of monomeric metal organochalcogenolates11–14 use phosphine,11 thiolate (S–R–S) 2– ,12 bulky chalcogenolate,13 and internally functionalized chalcogenolate ligands 14. The nitrogen donor site of the ligand stabilizes the coordination of the chalcogenolate with the Pd center 14d,14e. The use of N‐heterocycles is little known for this purpose; pyridyl and pyrimidyl groups are two examples 14d,14e.…”