ic9701930_si_001.cif (23.16 kB)

Synthesis, Molecular Structure, and Reactivity of the Tetranuclear Complex [NBu4]2[Pd4(μ-PPh2)2(μ-Cl)4(C6F5)4]. Molecular Structure of [Pd2(μ-PPh2)(C6F5)2(bipy)2]ClO4·C6H14§

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posted on 24.09.1997, 00:00 by Ester Alonso, Juan Forniés, Consuelo Fortuño, Antonio Martín, Georgina M. Rosair, Alan J. Welch
Anionic tetranuclear complexes with the molecular formula [NBu4]2[Pd4(μ-PPh2)2(μ-X)4(C6F5)4] [X = Cl (1), Br (2)] were obtained by reaction of [NBu4]2[Pd2(μ-PPh2)2(C6F5)4] and PdCl2 (or K2[PdCl4]) in acetone, followed by reaction with KBr for 2. The reactions of 1 with neutral monodentate (L) or bidentate (L-L) ligands afford the dinuclear derivatives [Pd2(μ-PPh2)(μ-Cl)(C6F5)2L2] [L = PPh3 (3), py (4)] or [Pd2(μ-PPh2)(C6F5)2(L-L)2]n [n = 1−, L-L = acac (6); n = 1+, L-L = bipy (7) or phen (8)]. The structures of complexes 1 and 7 were determined by single-crystal X-ray diffraction studies. The bis(acetone) solvate of complex 1, [NBu4]2[Pd4(μ-PPh2)2(μ-Cl)4(C6F5)4]·2C3H6O, crystallizes in the monoclinic system, space group P21/c, with a = 11.679(5) Å, b = 16.552(7) Å, c = 23.868(8) Å, β = 101.10(3)°, V = 4527.6(15) Å3, and Z = 2. The central core of the anion has the shape of a rectangle with the four Pd atoms in the corners. The hexane solvate of complex 7, [Pd2(μ-PPh2)(C6F5)2(bipy)2][ClO4]·C6H14, crystallizes in the monoclinic system, space group P21/n, with a = 16.214(3) Å, b = 10.311(2) Å, c = 28.380(6) Å, β = 100.82(3)°, V = 4660(2) Å3, and Z = 4. In both complexes, the long Pd···Pd distances (>3.1 Å) clearly point to the absence of any Pd−Pd interaction.

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