Abstract
The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1)°, V = 5243.2(11)' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.
| Original language | English |
|---|---|
| Pages (from-to) | 6118-6123 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 34 |
| Issue number | 24 |
| Publication status | Published - 1995 |
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Synthesis and characterization of dinuclear palladium complexes with bridging selenide or selenoxide ligands, including X-ray characterization of anti-Pd2Cl2(μ-Se)(μ-dpmMe)2 [dpmMe = 1,1-bis(diphenylphosphino)ethane]. / Besenyei, Gábor; Párkányí, L.; Simandi, Laszlo I.; James, Brian R.
In: Inorganic Chemistry, Vol. 34, No. 24, 1995, p. 6118-6123.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Synthesis and characterization of dinuclear palladium complexes with bridging selenide or selenoxide ligands, including X-ray characterization of anti-Pd2Cl2(μ-Se)(μ-dpmMe)2 [dpmMe = 1,1-bis(diphenylphosphino)ethane]
AU - Besenyei, Gábor
AU - Párkányí, L.
AU - Simandi, Laszlo I.
AU - James, Brian R.
PY - 1995
Y1 - 1995
N2 - The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1)°, V = 5243.2(11)' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.
AB - The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1)°, V = 5243.2(11)' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.
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M3 - Article
AN - SCOPUS:0007492409
VL - 34
SP - 6118
EP - 6123
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 24
ER -