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).
In the crystal structure of the title compound, C9H13BO2·C18H15OP, there are O—H⋯O hydrogen bonds between the O atom of triphenylphosphine oxide and one hydroxy group of the boronic acid. Boronic acid molecules form inversion-related hydrogen-bonded dimers in an R
2
2(8) motif. The structure is consolidated by intermolecular C—H⋯O bonds and C—H⋯π interactions.
Key indicators: single-crystal X-ray study; T = 297 K; mean (C-C) = 0.006 Å; disorder in main residue; R factor = 0.035; wR factor = 0.078; data-to-parameter ratio = 14.5.In the title compound, [Sb(C 9 H 12 N) 2 Cl], the Sb atom adopts a É-trigonal-bipyramidal geometry. The two 2-[(dimethylamino)methyl]phenyl ligands are coordinated asymmetrically to the Sb atom. The carbon atoms of one of the ligands are disordered over sets of sites with equal occupancy, resulting in two conformational isomers in the crystal. The Sb-C and Sb-N distances in the ordered ligand are: 2.153 (4) and 3.326 (5) Å , respectively. The corresponding distances in the disordered ligand are: 2.103 (5)/2.188 (5) and 2.454 (3) Å , respectively. The structure displays intramolecular C-HÁ Á ÁCl hydrogen bonding.
Related literature
ExperimentalCrystal data [Sb(C 9
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