title: Divalent heteroleptic ytterbium complexes--effective catalysts for intermolecular styrene hydrophosphination and hydroamination.
abstract: New heteroleptic Yb(II)-amide species supported by amidinate and 1,3,6,8-tetra-tert-butylcarbazol-9-yl ligands [2-MeOC6H4NC(tBu)N(C6H3-iPr2-2,6)]YbN(SiMe3)2(THF) (6) and [1,3,6,8-tBu4C12H4N]Yb[N(SiMe3)2](THF)n (n = 1 (7), 2 (8)) were synthesized using the amine elimination approach. Complex 6 features an unusual κ(1)-N,κ(2)-O,η(6)-arene coordination mode of the amidinate ligand onto Yb(II). Complexes 7 and 8 represent the first examples of lanthanide complexes with π-coordination of carbazol-9-yl ligands. Complexes 6 and 7, as well as the amidinate-Yb(II)-amide [tBuC(NC6H3-iPr2-2,6)2]YbN(SiMe3)2(THF) (5), are efficient precatalysts for the intermolecular hydrophosphination and hydroamination of styrene with diphenylphosphine, phenylphosphine, and pyrrolidine to give exclusively the anti-Markovnikov monoaddition product. For both types of reaction, the best performances were observed with carbazol-9-yl complex 7 (TONs up to 92 and 48 mol/mol at 60 °C, respectively).
authors.affiliation: G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences , Nizhny Novgorod, Russia.
authors.forename: Ivan V
authors.initials: IV
authors.lastname: Basalov
authors.forename: Sorin Claudiu
authors.initials: SC
authors.lastname: Roşca
authors.forename: Dmitry M
authors.initials: DM
authors.lastname: Lyubov
authors.forename: Alexander N
authors.initials: AN
authors.lastname: Selikhov
authors.forename: Georgy K
authors.initials: GK
authors.lastname: Fukin
authors.forename: Yann
authors.initials: Y
authors.lastname: Sarazin
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Carpentier
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Trifonov