Abstract
Cymantrene-based tris(1-pyrazolyl)borates have been synthesised from the reaction of CymBBr2 and Cym′BBr2 with pyrazole (Hpz) in the presence of triethylamine [Cym: cymantrenyl; Cym′: (methyl)cymantrenyl]. The Tl(I) salts CymB(pz)3Tl, 2a, and Cym′B(pz)3Tl, 2b, have been structurally characterised by X-ray crystallography. Similar to the corresponding complex FcB(pz)3Tl (Fc: ferrocenyl), CymB(pz)3Tl features a polymeric structure with bridging [B(pz)3] fragments in the solid state. Cym′B(pz)3Tl shows a related oligomeric structure. This time a macrocyclic tetramer rather than a linear chain is observed. To provide a ligand of high solubility in non-polar solvents, compound Cym′B(pz4-R)3Tl, [R = CH2(C6H11)] 2d, has been synthesised, which shows a reduced symmetry at the organometallic moiety, together with (cyclohexyl)methyl substituents in the 4-positions of all pyrazolyl rings.
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