Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 10, Pages 3361-3369Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201504411
Keywords
dearomatisation; metallacycles; metallocenes; pyridines; reduction
Categories
Funding
- DFG [RO 1269/9-1]
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Reactions of group4 metallocene sources with 2-substituted pyridines were investigated to evaluate their coordination type between innocent and reductive dearomatisation as well as to probe the possibility for couplings. A dependence on the cyclopentadienyl ligands (Cp, Cp*), the metals (Ti, Zr), and the substrates (2-phenyl-, 2-acetyl-, and 2-iminopyridine) was observed. While 2-phenylpyridine is barely reactive, 2-acetylpyridine reacts vigorously with the Cp-substituted complexes and selectively with their Cp* analogues. With 2-iminopyridine, in all cases selective reactions were observed. In the isolated [Cp2Ti], [Cp2Zr], and [Cp*Zr-2] compounds the substrate coordinates by its pyridyl ring and the unsaturated side-chain. Subsequently, the pyridine was dearomatised, which is most pronounced in the [Cp*Zr-2] compounds. Using [Cp*Ti-2] leads to the unexpected paramagnetic complexes [Cp*Ti-2(III)(N,O-acpy)] and [Cp*Ti-2(III)(N,N-impy)]. This highlights the non-innocent character of the pyridyl substrates.
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