Secondary interactions in decachloro-closo-decaborates R2[B10Cl10] (R = Et3NH+, Ph4P+, and [Ag(NH3)2]+): 35Cl NQR, PW-DFT, and X-ray studies

Synthesis of Perchlorinated Sulfonium Derivatives of closo-Decaborate Anion [2-B10Cl9SR2]− (R = i-C3H7, n-C3H7, n-C4H9, n-C8H17, n-C12H25, n-C18H37, CH2Ph, and cyclo-S(CH2)4)

“…The B–Cl bond lengths for the apical boron atoms B1 and B10 fall in the range of 1.778(2)–1.788(2) Å, which is noticeably shorter than the corresponding bonds for the equatorial boron atoms B3–B9 lying in the range of 1.796(2)–1.804(3) Å. This is consistent with the bond lengths for the unsubstituted anion in salt ((C 6 H 5 ) 4 P) 2 [B 10 Cl 10 ] . The B–S bond lengths are in the range of 1.88(1)–1.92(1) Å, which corresponds to similar bonds in other derivatives of the closo -decaborate anion of the sulfonium type …”

“…We have previously undertaken a systematic study of a capability of Cl atoms in perchlorinated [B 10 Cl 10 ] 2– anions to form intermolecular (noncovalent) bonds with cations and ligands using 35 Cl NQR and X-ray diffraction. ,− The current concept of noncovalent interaction, involving the atom (chlorine) bound by a covalent bond to another atom (boron), assumes that an area of depleted electron density (the σ-hole) is formed on the elongation of the covalent bond . This area attracts electron-donating sites (nucleophiles) hence forming a noncovalent bond.…”

“…Noncovalent closed-shell interactions C–H···π, π···π, p···π, and C–H···H–C were detected in [B 10 Cl 10 ] 2– clusters using 35 Cl NQR. ,− , The values of effective charges on chlorine atoms and the difference in occupation of their p π orbitals were evaluated in some of them. This allowed to get an idea about the extent of charge transfer as a result of noncovalent interactions.…”

Solvent-Induced Encapsulation of Cobalt(II) Ion by a Boron-Capped tris-Pyrazoloximate

“…The reagents used, Co­(NO 3 ) 2 ·6H 2 O, phenylboronic acid, hexafluoroacetone, tetra­( n -butyl)­ammonium chloride, N , N ′-dimethylurea, tetramethylurea, NaHCO 3 , and organic solvents, were obtained commercially (SAF). The pyrazoloxime ligand PzOxH and the initial salt ((C 2 H 5 ) 3 NH) 2 (B 10 Cl 10 ) were prepared as described elsewhere. , …”