Nucleophilic addition to ruthenium activated tetramethylthiophene

Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity

“…Similar to the reaction 86 of (η 6 -cymene)Ru(η 5 -Me 4 T) 2+ with NH 3 to give (η 6 -cymene)Ru(η 4 -Me 4 T·NH 2 ) + , (κ 3 -[9]aneS 3 )Ru(η 5 -Me 4 T) 2+ , where [9]aneS 3 is 1,4,7-trithiacyclononane, reacts with EtO - to give the analogous thioallyl complex (κ 3 -[9]aneS 3 )Ru(η 4 -Me 4 T·OEt) + , whose structure established by an X-ray diffraction study shows that the OEt - has added to carbon-2 and the other three carbons and sulfur remain bonded to the metal as in the related (OC) 3 Mn(η 4 -T·Nuc) complexes (eq 28) . Cleavage of the C−S bond does not occur, in contrast to reactions (eq 30) of the more electron-rich CpRu(η 5 -T*) + complexes with nucleophiles (including OEt - ), which give butadienethiolate complexes CpRu(η 5 -T*·Nuc).…”

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“…The lipophilic ligands L [32][33][34][35][36][37][38][39][40][41] form dinuclear complexes of general formula [(L [32][33][34][35][36][37][38][39][40][41] )Mn IV (m-O) 3 Mn IV (L [32][33][34][35][36][37][38][39][40][41] )] 2+ which, as the hexafluorophosphate salts, are soluble in dichloromethane solution. 29 These complexes have been used as epoxidation catalysts under biphasic conditions for lipophilic substrates such as styrene and decene.…”

“…L 55 reacts with [{Ru II (h 5 -TMT)(m-Cl)(Cl)} 2 ] to yield the mixed sandwich complex [Ru II (h 5 -TMT)(L 55 )] 2+ (TMT = tetramethylthiophene). 40 This material subsequently reacts with ethoxide to yield an adduct [Ru II (h 4 -TMT-2-OEt) (L 55 )] in which the ethoxide anion has attacked the co-ordinated thiophene fragment at the 2 position. In a crystallographic study the structures of the Group 8 half-sandwich compounds [Ru II (h 5 -C 5 H 5 )(L 55 )]PF 6 , [Ru II (h 5 -C 5 H 5 ) (L 59 )]PF 6 and [Fe II (h 5 -C 5 H 5 )(L 59 )]PF 6 have been determined.…”