Crystal structures of six complexes of phosphane chalcogenides R 1 R 2 R 3PE (R = tert-butyl or isopropyl, E = S or Se) with the metal halides MX 2 (M = Pd or Pt, X = Cl or Br), two halochalcogenylphosphonium derivatives ( t Bu2 iPrPEBr)2[Pd2Br6] and one hydrolysis product
Year: 2025
Type: article
Abstract: The L 2 MX 2 complexes 1–5 (1: L = t BuiPr2PSe, M = Pd, X = Cl; 2: L = t Bu2 iPrPSe, M = Pd, X = Cl; 3: L = t Bu2 iPrPSe, M = Pd, X = Br; 4: L = t Bu2 iPrPS, M = Pd, X = Br; 5: L = t Bu2 iPrPS, M = Pt, X = Cl) {systematic names: (tert-butyldiisopropylphosphine selenide-κSe)dichloridopalladium(II), [PdCl2(C10H23PSe)2] (1), (di-tert-butylisopropylphosphine selenide-κSe)dichloridopalladium(II), [PdCl2(C11H25PSe)2] (2), dibromido(di-tert-butylisopropylphosphine selenide-κSe)palladium(II), [PdBr2(C11H25PSe)2] (3), dibromido(di-tert-butylisopropylphosphine sulfide-κS)palladium(II), [PdBr2(C11H25PS)2] (4), dichlorido(di-tert-butylisopropylphosphine sulfide-κS)palladium(II), [PdCl2(C11H25PS)2] (5)} all display a trans configuration with square-planar geometry at the metal atom. Compounds 2 and 3 are isotypic. The molecules of 1 and 4 display crystallographic inversion symmetry; compound 5 involves two independent molecules, each with inversion symmetry but with differing orientations of the trialkylphosphane groups. Chemically equivalent bond lengths all lie in narrow ranges, whereby the values for palladium and platinum compounds scarcely differ. Compound 6, ( t BuiPr2PS)2Pd2Cl4 {systematic name: di-μ-chlorido-bis[(tert-butyldiisopropylphosphine sulfide-κS)chloridopalladium(II)], [PdCl2(C10H23PS)2]}, is dinuclear with a central Pd2Cl2 ring, and displays crystallographic inversion symmetry. The bonds to the bridging are longer than those to the terminal chlorine atoms; the Pd—S bond is shorter than the M—S bonds in 4 and 5, reflecting the weaker trans influence of (bridging) chlorine compared to sulfur. Compounds 7 and 8, 2( t Bu2 iPrPEBr)+ [Pd2Br6]2− with E = S for 7 and Se for 8 {systematic names: (bromosulfanyl)di-tert-butylisopropylphosphanium di-μ-bromido-bis[dibromidopalladium(II)], (C11H25BrPS)2[Pd2Br6] (7) and (bromoselanyl)di-tert-butylisopropylphosphanium di-μ-bromido-bis[dibromidopalladium(II)], (C11H25BrPS2)2[Pd2Br6], (8)}, were obtained by oxidizing the appropriate PdII precursors with elemental bromine; they are not isotypic. The ions are connected by very short halogen bonds Br...Br. For both compounds, two E...Br contacts further link the cations and anions to form ribbons. Compound 9 {systematic name: bis[dimethyl(sulfanylidene)phosphinito-κSe]bis(hydroxydiisopropylphosphine selenide-κSe)palladium(II), [Pd(C6H14OP)2(C6H15OP)2], {(iPr2PSeO)2H}2Pd, is a hydrolysis product with inversion symmetry and contains an intramolecular P—O...H—O—P group with a disordered hydrogen atom. Compounds 1–6 and 9 show few, if any, short intermolecular contacts, although some H...M contacts are observed. A problem with atom-type assignment for structure refinement is discussed.
Authors: Daniel Upmann, Peter G. Jones
Institution: Technische Universität Braunschweig
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $500
OpenAlex ID: W4407116336