153147-75-2Relevant articles and documents
Reactivity of tetramethylpyrrole complexes of ruthenium and osmium
Kvietok,Allured,Carperos,DuBois
, p. 60 - 68 (2008/10/08)
Reaction of [(p-cymene)M(OTf)2]x with tetramethylpyrrole leads to the formation of [(p-cymene)M(NC4Me4)]OTf, 1 when M = Ru, 2 when M = Os. Complex 1 crystallized in space group P212121 with unit cell dimensions a = 8.928(2) A, b = 13.772(4) A, c = 17.272(6) A, V = 2123.7(11) A3, and Z = 4. The crystal structure establishes that 1 is a sandwich complex with η6-cymene and η5-pyrrolyl ligands. Reaction of 1 or 2 with excess methyl triflate results in alkylation of the pyrrole nitrogen to form (η6-p-cymene)M(η5-MeNC4Me4)](OTf)2, 3 when M = Ru and 4 when M = Os. Reactions of 1 or 2 with LiAl(O-t-Bu)3H result in nucleophilic attack of hydride on the cymene ligand to form (η6-cymH)M(η5-NC4Me4), 5 when M = Ru, 6 when M = Os. Complexes 5 and 6 have been identified by one and two dimensional 1H NMR spectroscopy. Nucleophilic attack on the cymene ligand of 1 and 2 appears to be quite general, and the products of methoxide addition, (η5-cymOMe)M(η5-NC4Me4) 7 when M = Ru, 8 when M = Os have also been characterized by 1H NMR data. In contrast, reactions of the pentamethylpyrrole complexes 3 and 4 with nucleophiles lead to nucleophilic addition to the pentamethylpyrrole ligand. For example, the reaction of 3 with LiAl(O-t-Bu)3H resulted in the formation of [η6-p-cymene)Ru(η4-MeNC4Me4H)OTf, 10, which was characterized by an X-ray diffraction study. 10 crystallized in space group P21c with a = 8.153(2) A, b = 17.351 (2) A, c = 16.508(2) A, β = 104.396(13)°, V = 2261.9(7) A3, and Z = 4. The structure established that the hydride nucleophile added to an α carbon of the pentamethylpyrrole ligand in an exo orientation. This α carbon lies out of the plane of the remaining four ring atoms with a dihedral angle of 38°. The modified pentamethylpyrrole ligand coordinates to Ru in a η4-coordination mode. Further reaction of 10 with protic acid leads to further pyrrole reduction and dissociation from the metal. The reactions of the pyrrole systems are compared to those of related [(arene)Ru(thiophene)]n+ derivatives.