Systematics of palladium(II) and platinum(II) dithioether complexes. The effect of ligand structure upon the structure and spectra of the complexes and upon inversion at coordinated sulphur

Solution, Structural and Catalytic Studies of Neutral MCl2 (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH2)C5H4N(RE = MeS, PhS, MeSe)

“…Similar trends in bond distances in isomorphous structures of palladium and platinum complexes containing homoleptic and heteroleptic ligands have been observed, and theoretical calculations have been performed to explain the trend. [14][15][16][17][18][19] Results from theoretical calculations for the geometry optimisations of the complexes [MMe 3 {(H 2 C=N-NH) 3 CH}] + compared well with the X-ray studies of isostructural [MMe 3 {(pz) 3 -CH}] + (M = Pd, Pt), where the M-C bond distances are identical or slightly shorter for palladium and platinum while the Pd-N bonds are longer than the Pt-N bonds. [19] The explanation for this trend is attributed to the softer acidity of platinum compared with palladium.…”

“…This occurs at lower catalyst loadings relative to other similar reactions reported in the literature. [21,22] Fu and Littke have reported the reaction of deactivated aryl bromides with methyl trans-cinnamate at room temperature achieving 80 % isolated yield after 72 h with Ͼ20:1 E/Z selectivity by using 1.0 mol-% Pd 2 (dba) 3 and 2.0 mol-% P(tBu) 3 . [21] Scheme2.…”

“…Palladium(ii) and platinum(ii) complexes containing dithioether ligands have been extensively studied in recent years, [1][2][3] leading to an understanding of the S-pyramidal inversion process in solution. Reports of similar compounds containing diselenoether and ditelluroether ligands are now more prevalent and include solution properties ascertained by using multinuclear NMR spectroscopy.…”

1,2,4,5-Tetrazine: Synthesis and Reactivity in [4+2] Cycloadditions

“…[22a] 42a؊c, [33] 42d, [34] 42e, [35] 42f [36] 43b, [37] 43c, [38] 45a [ , 39] (80°C) of ethyl vinyl ether (41b, 2.25 g, 31.2 mmol) in dioxane 48c, [40] 48e, [41] 49a, [42] 49b, [43] 50, [44] 51 [45] were prepared according (5 ml). The rate of addition was initially controlled by complete to published procedures.…”

Dinuclear niobium(III), tantalum(III) and tantalum(IV) complexes with thioether and selenoether ligands

“…Me2Se was obtained from Strem. n Bu2Se and the dithio-and diselenoethers were made by literature methods or minor modifications thereof [22].…”