Sc and Y Heteroalkyl Complexes with a NC_sp3N Pincer‐Type Diphenylmethanido Ligand: Synthesis, Structure, and Reactivity

Abstract

New diphenylmethane [4‐tBu‐2‐(C3H2N2Me‐1)C6H3]2CH2 (1) bearing pendant imidazolyl groups in ortho‐positions of aromatic rings of diphenylmethane skeleton was synthesized using Stille cross‐coupling reaction between bis(4‐(tert‐butyl)‐2‐iodophenyl)methane and Bu3Sn(C3H2N2Me) in the presence of Pd(PPh3)4. Potassium diphenylmethanide [{[4‐tBu‐2‐(C3H2N2Me‐1)C6H3]2CH}K(OEt2)]2 (2K) was prepared by treatment of 1 with an equimolar amount of Lochmann‐Schlosser super base. Rare‐earth metal heteroalkyl complexes {[4‐tBu‐2‐(C3H2N2Me‐1)C6H3]2CH}Ln(CH2SiMe3)2(THF)n (Ln = Sc, n = 0 (2Sc); Y, n = 1 (2Y)) with NCsp3N pincer type diphenylmethanido ligand were synthesized by the selective sp3 CH‐bond activation of the central CH2 group in 1 by Ln(CH2SiMe3)3(THF)2. According to the X‐ray data the diphenylmethanido ligands in 2K and 2Sc perform a tridentate pincer‐type κ3‐N,C,N coordination. Complexes 2Ln were evaluated as catalysts for isoprene polymerization and hydrosilylation of alkenes and alkynes.

Synthesis, X-ray Structure, Hirshfeld Analysis of Biologically Active Mn(II) Pincer Complexes Based on s-Triazine Ligands

“…In continuation to our interest with the s-triazine pincer complexes [21][22][23][24], and in light of the interesting recently reported data in literature [25][26][27][28][29][30][31], we are presenting here the synthesis of two new Mn(II) complexes with the s-triazine based NNN-pincer ligands shown in Figure 1. The structural In continuation to our interest with the s-triazine pincer complexes [21][22][23][24], and in light of the interesting recently reported data in literature [25][26][27][28][29][30][31], we are presenting here the synthesis of two new Mn(II) complexes with the s-triazine based NNN-pincer ligands shown in Figure 1. The structural features of both complexes are elucidated.…”

Synthesis, Characterization, and Reactivity Studies of New Cyclam-Based Y(III) Complexes

“…In this context, yttrium complexes have attracted much attention due to their high reactivity in intramolecular hydroamination [2][3][4][5][6][7][8][9][10] as well as olefin [11][12][13][14] and cyclic ester [15][16][17][18][19][20] polymerization catalysis. The hard Lewis acid nature of yttrium explains its tendency to coordinate to ligands that contain oxygen and nitrogen donors [21][22][23][24][25][26][27][28]. Although a rich chemistry of delocalized systems possessing aminato, guanidinato, and β-diketiminato ligands have emerged, chelating dianionic diamido ligands with located charges seemed to be depreciated and far from reaching those levels of importance.…”