Synthesis and Molecular Structures of the Base-stabilized Arylboron Dichlorides BCl₂{2,6-(NEt₂CH₂)₂C₆H₃} and BCl₂{2-(NMe₂CH₂)C₆H₄}

Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton − Elucidation of Hypervalent Interaction Based on X-ray Analysis and DFT Calculation

“…It was similar to the behavior of 54 (Figure ) 9 in 1 H NMR, which showed only one singlet (12H) of the two NMe 2 groups and maintained its sharpness in CD 2 Cl 2 from 25 °C to −100 °C. However, it was contrasted with the behavior of BCl 2 [2,6-(Et 2 NCH 2 ) 2 C 6 H 3 ] ( 55 , Figure ) in 1 H NMR, which showed two kinds of NEt 2 groups in C 6 D 6 or THF- d 8 solvents at 25 °C. The NMR data of 52 indicates that the very rapid “bond-switching” accompanied with the inversion at the central atom (bell-clapper rearrangement) 12 is taking place in solution as illustrated in Scheme .…”

Deprotonation from an N-Methyl Group in 2-[1-(Dimethylamino)-1-methylethyl]phenylborane Derivatives

“…Recently, we revealed that the amine ligand in 2-[1-(dimethylamino)-1-methylethyl]phenyl group 1 (Ar*) coordinated to the attaching boron atom more tightly than that in 2-[1-(dimethylamino)methyl]phenyl group 2 (Ar) (Chart ), on the basis of kinetic data. − By using the bulky C , N -bidentate ligand 1 , we attempted to prepare sterically congested organoboron complexes, for instance BAr* 2 X and BAr* 3 , from the structural and stereodynamic interests . However, the reaction of a trialkyl borate with an appropriate amount of Ar*Li yielded no desired compounds but an unexpected compound ( 7 ), in which one of the N -Me carbons was bonded to the boron atom, as a major product: this type of product has never been reported in the series of studies of the intramolecular organoboron complexes to our knowledge. − , This paper is to report the identification of the new heterocyclic product and a plausible mechanism of its formation, in which deprotonation from an N -Me group is the key step.…”

Synthesis of a Novel Potential Tridentate Anthracene Ligand, 1,8-Bis(dimethylamino)-9-bromoanthracene, and Its Application as Chelate Ligand for Synthesis of the Corresponding Boron and Palladium Compounds

“…Since the energy barrier of the NB bond‐switching process in 11 c was too small to measure by coalescence method, the energy difference between the unsymmetrical tetracoordinate dichloroboron 11 c and the pentacoordinate one 11 c ≠ , which should be the transition state of the bond‐switching process, named the “bell‐clapper” mechanism,12 must be very small (Scheme ). The result is in contrast to the relatively high energy barrier of the similar S N 2 type reaction of BCl 2 [2,6‐(NEt 2 CH 2 ) 2 C 6 H 3 ] ( 12 ),13a which showed two kinds of NEt 2 groups in C 6 D 6 or [D 8 ]THF at 25 °C…”