Nucleophilic addition reactions to nitrilium derivatives [B₁₂H₁₁NCCH₃]⁻ and [B₁₂H₁₁NCCH₂CH₃]⁻. Synthesis and structures of closo-dodecaborate-based iminols, amides and amidines

Abstract

The synthesis of the acetonitrilium and propioitrilium derivatives of closo-dodecaborate [B12H12]2- were discussed. The nucleophilic addition reactions of water, alcohols and secondary amines to the activated triple bond of the...

Charge-compensated nido-carborane derivatives in the synthesis of iron(ii) bis(dicarbollide) complexes

“…The preparation of an unprotonated amide derivative of iron bis(dicarbollide) at first glance contrasts with the formation of protonated forms of amide derivatives (iminols) of other polyhedral boron hydrides. 29 c ,37–39 The reason for this may be the much lower basicity of amides 40 compared with amidines, 41 which leads to the ease of deprotonation of the iminol and a decrease in the electron-withdrawing effect of the substituent. As a result, the oxidation of iron( ii ) to iron( iii ) occurs more easily.…”

New Aspects of the Synthesis of closo-Dodecaborate Nitrilium Derivatives [B12H11NCR]− (R = n-C3H7, i-C3H7, 4-C6H4CH3, 1-C10H7): Experimental and Theoretical Studies

“…Nitrilium derivatives have been obtained for closo-decaborate [36][37][38][39][40], cobalt bis-dicarbolide [41][42][43][44] and nido-carborane systems [45][46][47][48]. Several approaches to the preparation of these systems have been established.…”

“…In several works, nitrilium derivatives of closo-dodecaborate anions were prepared [B 12 H 11 NCR] − , R = CH 3 , CH 2 CH 3 [40,52] and different reaction protocols were applied. In paper [52], the most optimal method was established.…”

Carboxonium derivatives based on closo-dodecaborate anions [1,2-B12H10O2CR]−: synthesis and molecular orbital analysis

“…37,38 Molecular systems based on the closo-dodecaborate anion have found applications in a variety of spheres, such as medicine (boron neutron capture therapy), electrode materials, photoredox catalysis, fluorescent materials, etc. [39][40][41][42][43][44][45][46] Thus, the preparation and investigation of the properties of carboxonium derivatives of the general form [1,2-B 12 H 10 O 2 CR] À are a specific topic in modern boron chemistry. In the current work, the focus was on a search for a means of synthesising the target carboxonium derivatives and a theoretical investigation of the nature of the interaction between the exo-polyhedral substituent and the cluster cage.…”