From Borane to Borylene without Reduction: Ambiphilic Behavior of a Monovalent Silylisonitrile Boron Species

Triaminotriborane(3): A Homocatenated Boron Chain Connected by B−B Multiple Bonds

“…At −80 °C, the 11 B NMR spectrum showed two broad signals at δ =−4.8 and 77.6 ppm (half‐width h 1/2 =1700 and 6200 Hz, respectively), assigned to the central and terminal boron nuclei of 2 , respectively. The negative chemical shift of δ =−4.8 ppm is comparable to those of nucleophilic Lewis base stabilized borylenes (−32.2–0.8 ppm) ,,,,,,,. The chemical shift δ =77.6 ppm is comparable to those of low‐coordinate silaborene and azaborataallene, and the quite large half‐width is similar to that of dimesitylborinium cation ( h 1/2 =5000 Hz) .…”

Reduction of a dihydroboryl cation to a boryl anion and its air-stable, neutral hydroboryl radical through hydrogen shuttling

“…This is indicative of strong p backdonation from the lone pair of the boryl anion to the p-accepting CAAC Me ligand, as found in all CAAC-stabilised boryl anions. 6,[14][15][16][17] According to DFT calculations carried out at the uB97XD/6-31+G* level of theory, the HOMO of 5 possesses p-bonding character between B1 and C1A, with a nodal plane located at the C1A-N1 0 bond region (Fig. 4).…”

“…1a), [5][6][7][8][9][10] boryl radical cations ([(CAAC)LBY]c + , L ¼ Lewis donor) [10][11][12][13] and boryl anions ([(CAAC)BXY] À , e.g. II), [14][15][16][17] as well as boron(I) species such as borylenes ((CAAC)LBX, e.g. III, and (CAAC)BNR 2 ).…”

“…III, and (CAAC)BNR 2 ). [6][7][8][11][12][13]16,[18][19][20] In all these compounds, the accumulation of negative charge on the low-valent boron centre is stabilised through p backbonding to the CAAC ligand(s) ( Fig. 1a), making many of them surprisingly stable under inert conditions.…”

Crystalline Boragermenes

“…TheB1-Ge1-C13 and Si3-N2-Si4 planes are nearly perpendicular to each other (79.748 8). TheGe1ÀB2 (1.911 7)bond is much shorter than that of 2 (2.122 7), as well as typical GeÀBs ingle bonds (2.045-2.165 ), [16] which is indicative of am ultiple bond character between the Ge1 and B2 atoms.T he Ge1 À B1 (2.029 7) and N2 À B2 (1.358(8) )bonds of 3 are shorter than those of 2 (Ge1-B1 2.109 7, N2-B2 1.394 9), suggesting enhanced interactions between those atoms.…”