Inorganic Chemistry, Vol.37, No.23, 6060-6064, 1998
Synthesis of a metallaborane complex containing Pd(III) and the first doubly charge compensated ollide ion. X-ray crystal structure of 1,4-Br-2-1,2,5-(PMe2Ph)(3)-closo-1-PdB11H8
The reaction of [Me3NH][nido-B11H14] with 4 equiv of lithium alkyl in THF at 5 degrees C generated the putative ollide ion, Li-4[B11H11], which was not isolated. This was treated in situ with (PMe2Ph)(2)PdBr2 to yield the metallaborane 1,4-Br-2-1,2,5-(PMe2Ph)(3)-closo-1-PdB11H8. This metallaborane contains the first doubly charge compensated ollide ion. It was isolated in low yield from the reaction mixture by chromatography. Characterization of this air-stable palladium ollide complex by magnetic susceptibility, EPR, and CV confirmed that it contains Pd(III) and is paramagnetic. It was also characterized by an X-ray diffraction study of a single crystal. The sample consisted of rust-colored crystals of monoclinic space soup P2(1)/c, with a = 9.749(13) Angstrom, b = 16.30(2) Angstrom, c = 21.65(3) Angstrom, beta = 97.21(4)degrees, and Z = 4. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0730 (5172 reflections), R-w = 0.0620.
Keywords:MACROCYCLIC COMPLEXES;PALLADIUM;1;4;10;13-TETRATHIA-7;16-DIAZACYCLO-OCTADECANE;ELECTROCHEMISTRY;CHEMISTRY;NICKEL