ic4027859_si_002.zip (25.57 kB)
Divalent Heteroleptic Ytterbium Complexes – Effective Catalysts for Intermolecular Styrene Hydrophosphination and Hydroamination
dataset
posted on 2014-02-03, 00:00 authored by Ivan V. Basalov, Sorin
Claudiu Roşca, Dmitry M. Lyubov, Alexander N. Selikhov, Georgy K. Fukin, Yann Sarazin, Jean-François Carpentier, Alexander A. TrifonovNew
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
κ1-N,κ2-O,η6-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).
