Nickel and Palladium Complexes of a PP(O)P Pincer Ligand Based upon a peri-Substituted Acenaphthyl Scaffold and a Secondary Phosphine Oxide

Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity

“…While bismuth cations with neutral donor ligands and [PF 6 ] À counteranions such as [BiPh 2 (NC 5 H 5 ) 2 ] + are accessible, [25] our results indicate that [PF 6 ] À is not a suitable anion for the preparation of donor-free organobismuth cations. These experimental findings are in line with previously reported theoretical calculations, which assigned a fluoride ion affinity (FIA) of 602 to [Bi(2,6-Mes 2 C 6 H 3 ) 2 ] + (level of theory: B3PW91/6-311 + G(2df,p)), [26] surpassing the FIA of 384 found for PF 5 (level of theory: DLPNO-CCSD(T)/aug-cc-pVQZ). [27] In order to obtain indications of the in situ-formation of 1 Dipp in solution we attempted to trap reactive intermediates with OPEt 3 , which subsequently yielded [BiDipp 2 (OPEt 3 ) 2 ][PF 6 ] (3 Dipp ) as a colorless crystalline solid.…”

Rapid, iterative syntheses of unsymmetrical di- and triarylboranes from crystalline aryldifluoroboranes

“…The crystal structures of 3 at 150 K (Fig. 1, top), rened to high accuracy using non-spherical atomic scattering factors (see the ESI †), reveal B-F bonds shorter than in BF 3 (in Å, 1.26-1.31), 28 similar to previously reported ArBF 2 (1.307(2)- 1.3146(15)), 29,30 B-BF 2 (1.24(3)-1.359( 5)), [31][32][33][34] and Pt-BF 2 (1.324(7)-1.344(4)) 32,[35][36][37] systems, but contracted in comparison to [ArBF 3 ] − , e.g., [N( n Bu) 4 ][PhBF 3 ] (1.409(3)-1.426(2)). 38 When ordered in terms of steric bulk, the B-F bonds elongate only subtly from 3h (least hindered) to 3a (most), but are signicantly shorter in 3b, comparably to EindBF 2 and TerBF 2 .…”

Kinetically Stabilized Diarylpnictogenium Ions

“…It was calculated for 7 and 8 and is compared to 1–6 (Figure 9). [77,92] The [R ind MesE] + series reveals slightly lower FIA values (639–559) than the [(2,6‐Mes 2 C 6 H 3 ) 2 E] + series (701–602); yet all values are considerably larger than 480 kJ mol −1 (SbF 5 ), which qualifies 1 – 8 as Lewis super acids.…”