“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐closo‐dodecaborate

Abstract

We designed, synthesized, and characterized two types of dimeric forms of monocarba-closo-dodecaborate, namely, a "dumbbell"-shaped dianion having a C-C bond and a "clackers"-shaped monoanion having an iodonium linker. The unique architectures of these anionic molecules were established by X-ray analysis. Spectroscopic analysis, DFT calculations, and reactivity experiments revealed high anionic and chemical stability of both anions, which are crucial properties for weakly coordinating anions.

Thecloso‐Dodecaborate Dianion Fused with Oxazoles Provides 3D Diboraheterocycles with Selective Antimicrobial Activity

“…Table 2. [26,27] Diboraoxazoles 2 were also fully characterizedb yN MR spectroscopy( 1 H, 1 H{ 11 B}, 13 C{ 1 H}, 11 B, 11 B{ 1 H}, 11 B-11 BC OSY)a nd mass spectrometry.C rystals tructures were determined for 2a, 2l, 2m, 2o,a nd 2q.A sr epresentativee xamples, the structures of 2a and 2m will be discussed.I n2a,t he B1ÀN1 distance of 1.519 (4) is almost identical to that of 1o ( Figure 4). [a] Entry[ TM] [b] Additive [c] T limits the conversion.…”

Recent Progress in the Synthesis of the Monocarba‐closo‐dodecaborate(−) Anions

“…Recently, our group designed, synthesized, and characterized two types of novel weakly coordinating anions (WCAs) which had dimeric structural forms of 1 , namely, a “dumbbell”‐shaped dianion having a C−C bond 41 and a “clacker”‐shaped monoanion having an iodonium linker 42 (Figure ) …”

“…The synthesis of [(CB 11 H 11 ) 2 I] − 42 is also illustrated in Scheme . The structures of the “dumbbell”‐shaped C1 carborane dimer 41 and “clacker”‐shaped dicarboranyliodonium 42 were confirmed by X‐ray crystallographic analysis . Considering that properties of WCAs are dependent upon the molecular size and structure these novel molecules are expected to offer new opportunities for designing WCAs.…”

“…[25] Recently,our group designed, synthesized,a nd characterized two types of novel weakly coordinating anions (WCAs) which had dimerics tructuralf orms of 1,n amely,a"dumbbell"shaped dianion having aC ÀCb ond 41 and a" clacker"-shaped monoanion having an iodonium linker 42 (Figure 11). [26] We employedaoxidative homo-coupling reaction using copper(I) C1 carborane anion to obtain the CÀCvertex-coupled dianionic dimer 41 (Scheme13). The synthesis of [(CB 11 H 11 ) 2 I] À 42 is also illustrated in Scheme 13.…”

“Dumbbell”‐ and “Clackers”‐Shaped Dimeric Derivatives of Monocarba‐closo‐dodecaborate

“…Reed et al have developed ar eliable method to evaluate coordinating ability (or anionic stability) using IR analysis of tri-n-octylammonium salts. [14] Table 1: IR data of the tri-n-octylammonium salts. TheN ÀHs tretching vibration at 3138 cm À1 observed for 2 is comparable to that of the parent carborane anion 1 (3149 cm À1 )i nt he solid state, and is at higher frequency than that of dodecaborate dianion (1) Hydrogen atoms are omitted for clarity.T hermalellipsoids are set at 50 %p robability (C black, Bmagenta, Igreen, Porange).…”