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Crystal structures of six complexes of phosphane chalcogenides R1R2R3PE (R = tert-butyl or isopropyl, E = S or Se) with the metal halides MX2 (M = Pd or Pt, X = Cl or Br), two halochalcogenylphosphonium derivatives (tBu2iPrPEBr)2[Pd2Br6] and one hydrolysis product

Affiliation/Institute
Institut für Anorganische und Analytische Chemie
Upmann, Daniel;
GND
1132099900
Affiliation/Institute
Institut für Anorganische und Analytische Chemie
Jones, Peter G.

The L2MX2 complexes 15 (1: L = tBuiPr2PSe, M = Pd, X = Cl; 2: L = tBu2iPrPSe, M = Pd, X = Cl; 3: L = tBu2iPrPSe, M = Pd, X = Br; 4: L = tBu2iPrPS, M = Pd, X = Br; 5: L = tBu2iPrPS, 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, (tBuiPr2PS)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(tBu2iPrPEBr)+ [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 16 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.

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