title: Half-Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non-Conventional Sterically Governed Oxidation of (tBu4Carb)2Sm.
abstract: The half-sandwich tetra-tert-butylcarbazol-9-yl iodo complex [(tBu4Carb)Sm(μ-I)(THF)2]2(1) was synthesized by the salt metathesis reaction of tBu4CarbK and SmI2(THF)2in THF. Complex 1 along with metallic Cu was also isolated from the oxidation reaction of (tBu4Carb)2Sm by CuI. The formation of stable radical tBu4Carb.was detected in this non-conventional process, indicating preferential oxidation of anion tBu4Carb-vs. SmII. The treatment of 1 with two equivalents of dibenzo-18-crown-6 resulted in heterolytic dissociation of a η5-bond Sm-tBu4Carb and afforded an ionic compound [tBu4carb-][SmI(crown)(THF)2]+(4). Alkylation of 1 with o-NMe2C6H4CH2K (1:2 molar ratio) in THF allowed for the synthesis of half-sandwich SmIIalkyl complex (tBu4Carb)SmCH2(o-NMe2C6H4CH2)(THF)2(5) in 55 % yield. The amido complex (tBu4Carb)SmN(SiMe3)2(DME) (6) was obtained by the reaction of 1 with two molar equivalents of NaN(SiMe3)2in THF in 89 % yield.
authors.affiliation: Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, GSP-445, 630950, Nizhny Novgorod, Russia.
authors.forename: Alexander N
authors.initials: AN
authors.lastname: Selikhov
authors.affiliation: Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, GSP-445, 630950, Nizhny Novgorod, Russia.
authors.forename: Tatyana V
authors.initials: TV
authors.lastname: Mahrova
authors.affiliation: Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, GSP-445, 630950, Nizhny Novgorod, Russia.
authors.forename: Anton V
authors.initials: AV
authors.lastname: Cherkasov
authors.affiliation: Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, GSP-445, 630950, Nizhny Novgorod, Russia.
authors.forename: Georgy K
authors.initials: GK
authors.lastname: Fukin
authors.affiliation: Université de Toulouse, INSA, UPS, CNRS-UMR5215, LPCNO, Avenue de Rangueil 135, 31077, Toulouse, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.affiliation: Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, GSP-445, 630950, Nizhny Novgorod, Russia.|Institute of Organoelement compounds of Russian Academy of Sciences, Vavilova str. 28, 119334, Moscow, Russia.
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Trifonov
keywords: complexes; lanthanides; samarium; structure elucidation; synthesis