Synthesis, Molecular Structure, and Reactivity of the Tetranuclear Complex [NBu(4)](2)[Pd(4)(&mgr;-PPh(2))(2)(&mgr;-Cl)(4)(C(6)F(5))(4)]. Molecular Structure of [Pd(2)(&mgr;-PPh(2))(C(6)F(5))(2)(bipy)(2)]ClO(4).C(6)H(14).
Anionic tetranuclear complexes with the molecular formula [NBu(4)](2)[Pd(4)(&mgr;-PPh(2))(2)(&mgr;-X)(4)(C(6)F(5))(4)] [X = Cl (1), Br (2)] were obtained by reaction of [NBu(4)](2)[Pd(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and PdCl(2) (or K(2)[PdCl(4)]) 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 [Pd(2)(&mgr;-PPh(2))(&mgr;-Cl)(C(6)F(5))(2)L(2)] [L = PPh(3) (3), py (4)] or [Pd(2)(&mgr;-PPh(2))(C(6)F(5))(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, [NBu(4)](2)[Pd(4)(&mgr;-PPh(2))(2)(&mgr;-Cl)(4)(C(6)F(5))(4)].2C(3)H(6)O, crystallizes in the monoclinic system, space group P2(1)/c, with a = 11.679(5) Å, b = 16.552(7) Å, c = 23.868(8) Å, beta = 101.10(3) degrees, V = 4527.6(15) Å(3), 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, [Pd(2)(&mgr;-PPh(2))(C(6)F(5))(2)(bipy)(2)][ClO(4)].C(6)H(14), crystallizes in the monoclinic system, space group P2(1)/n, with a = 16.214(3) Å, b = 10.311(2) Å, c = 28.380(6) Å, beta = 100.82(3) degrees, V = 4660(2) Å(3), and Z = 4. In both complexes, the long Pd.Pd distances (>3.1 Å) clearly point to the absence of any Pd-Pd interaction.
Alonso
Ester
E
Departamento de Química Inorgánica and Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, and Department of Chemistry, Heriot-Watt University, Edinburgh EH14 4AS, U.K.
Forniés
Juan
J
Fortuño
Consuelo
C
Martín
Antonio
A
Rosair
Georgina M.
GM
Welch
Alan J.
AJ