2N framework electron clusters: diamagnetic polyhedral boron chlorides, BnCln (n = 8-12), from the thermal disproportionation of diboron tetrachloride

Davan, T.; Morrison, John A.

doi:10.1021/ic00234a018

Cited by 30 publications

(16 citation statements)

References 7 publications

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“…The first signal can be assigned to B 10 Cl 10 (63.2 ppm) since it is known that the thermal decomposition of B 2 Cl 4 yields -beside B 8 Cl 8 and B 9 Cl 9 -also the higher boron subchlorides, especially B 10 Cl 10 and B 11 Cl 11 . [6,20] The chemical shifts which we observed here and in similar experiments (63.2 ppm and 69.1 ppm, resp.) are in good agreement with the reported values for B 10 Cl 10 and B 11 Cl 11 .…”

Section: Synthesis and Properties Of B 8 CLsupporting

confidence: 85%

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B₈Cl₈, the Radical Anion hypercloso‐[B₈Cl₈]^.− and the Dianion closo‐[B₈Cl₈]²⁻

et al. 2021

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The synthesis, spectroscopic data, redox properties of B 8 Cl 8 , [B 8 Cl 8 ] *À , and [B 8 Cl 8 ] 2À , and the single-crystal X-ray structure analysis of [Ph 4 P] + 2 [B 8 Cl 8 ] 2À • CH 3 CN are described. Temperaturedependent 11 B NMR measurements and theoretical studies (DFT) concerning the fluxional behavior of [B 8 Cl 8 ] 2À will be discussed. -B 8 Cl 8 reacts with reductants like iodide to the intense purple colored radical anion [B 8 Cl 8 ] *À which is formed as well from B 8 Cl 8 by traces of water. The colorless dianion closo-[B 8 Cl 8 ] 2À is obtained by the reaction of B 8 Cl 8 or [B 8 Cl 8 ] *À with iodide. The single-crystal X-ray structure analysis of [Ph 4 P] + 2 [B 8 Cl 8 ] 2À confirms the dodecahedral D 2d structure of [B 8 Cl 8 ] 2À . The 11 B NMR spectra of [B 8 Cl 8 ] 2À solutions show only one broad signal even at low temperatures due to the fast fluctuation of the [B 8 Cl 8 ] 2À polyhedron. The energy of the C 2v structure isomer of [B 8 Cl 8 ] 2À was calculated by DFT methods to be only 0.6 kcal/ mol higher in energy than the D 2d form, and the activation barrier for the D 2d to C 2v transformation is predicted to be about 0.9 kcal/mol.

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Section: Synthesis and Properties Of B 8 CLsupporting

confidence: 85%

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B₈Cl₈, the Radical Anion hypercloso‐[B₈Cl₈]^.− and the Dianion closo‐[B₈Cl₈]²⁻

et al. 2021

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“…BBr 3 ein Gemisch verschiedener ho È herer Halogenboran-Cluster B n Cl n (n = 8±12) [12,41] bzw. B 2 Br 4 ergibt neben BCl 3 bzw.…”

Section: Professor Ekkehard Fluck Zum 70 Geburtstag Gewidmetunclassified

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Einholz¹,

Vaas²,

Wieloch³

et al. 2002

Z. anorg. allg. Chem.

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Professor Ekkehard Fluck zum 70. Geburtstag gewidmet Inhaltsu È bersicht. Die Oxidation der Decachlor-closodecaborate(2±) Cs 2 [B 10 Cl 10 ] oder [Me 4 N] 2 [B 10 Cl 10 ] mit Tl(CF 3 COO) 3 ergibt das Radikal-Monoanion hypercloso-[B 10 Cl 10 ]´±, das durch ESR-und UV/Vis-Spektroskopie charakterisiert wurde. [B 10 Cl 10 ]´± dimerisiert nicht wie [B 10 H 10 ]´±, es wird aber durch Acetonitril zum Dianion [B 10 Cl 10 ] 2± reduziert. Cs 2 [B 10 Cl 10 ] reagiert mit sta È rkeren Oxidationsmitteln wie CoF 3 (in Dichlormethan) oder XeF 2 (in Perfluorhexan) unter Bildung von B 9 Cl 9 und ± in Spuren ± B 8 Cl 8 . Im Gegensatz zu diesen Befunden zeigt der Decabrom-closo-decaborat-Cluster Cs 2 [B 10 Br 10 ] keine Reaktionen mit Tl(CF 3 COO) 3 in Acetonitril oder mit CoF 3 in CH 2 Cl 2 . Die Oxidation der Dianionen [B 10 X 10 ] 2± (X = Cl, Br) wurde durch elektroanalytische Methoden (Cyclovoltammetrie, Chronoamperometrie, Chronocoulometrie) untersucht. Fu È r die zwei Stufen der Reaktion wurden die Formalpotentiale bestimmt, die keinen Einfluû von Struktura È nderungen erkennen lassen. Die Struktur von Cs 2 [B 10 Br 10 ]´2 H 2 O wurde an einem Einkristall durch Ro È ntgendiffraktometrie bestimmt. Cs 2 [B 10 Br 10 ]2 H 2 O kristallisiert monoklin (Raumgruppe I 2/a (Nr. 15), Z = 8, a = 1361,54(9) pm, b = 1215,89(5) pm, c = 3108,4(2) pm, a = 90°, b = 97,916(8)°, c = 90°). Der closo-Cluster [B 10 Br 10 ] 2± hat die Struktur des zweifach u È berkappten quadratischen Antiprismas mit idealisierter D 4d -Symmetrie. Chemical and Cyclovoltammetric Investigation of the Redoxreactions of the Decahalodecaborates closo-[B 10 X 10 ] 2± and hypercloso-[B 10 X 10 ]´± (X = Cl, Br) 1) . Crystal Structure Analysis of Cs 2 [B 10 Br 10 ]´2 H 2 O Abstract. The oxidation of the decachloro-closo-decaborates(2±) Cs 2 [B 10 Cl 10 ] or [Me 4 N] 2 [B 10 Cl 10 ] with Tl(CF 3 COO) 3 leads to the corresponding radical monoanion hypercloso-[B 10 Cl 10 ]´±, which was characterized by ESR and UV/Vis spectroscopy. [B 10 Cl 10 ]´± does not dimerize like [B 10 H 10 ]´± but it is reduced by acetonitrile to the dianion [B 10 Cl 10 ] 2± . Cs 2 [B 10 Cl 10 ] reacts with stronger oxidation agents like CoF 3 (in dichloromethane) or XeF 2 (in perfluorhexane), respectively, to yield B 9 Cl 9 and, in traces, B 8 Cl 8 . In opposite to this, the decabromoderivative Cs 2 [B 10 Br 10 ] does not show any reaction with Tl(CF 3 COO) 3 in acetonitrile or with CoF 3 in CH 2 Cl 2 .The oxidation of the dianions [B 10 X 10 ] 2± (X = Cl, Br) was studied by electroanalytical methods (cyclic voltammetry, chronoamperometry, chronocoulometry). Formal potentials were determined for the two steps of the reaction, which do not seem to be affected by structural rearrangements.The crystal structure of Cs 2 [B 10 Br 10 ]´2 H 2 O was analyzed by single-crystal X-ray diffraction. Cs 2 [B 10 Br 10 ]´2 H 2 O crystallizes monoclinic (space group I2/a, (no. 15), Z = 8, a = 1361.54(9) pm, b = 1215.89(5) pm, c = 3108.4(2) pm, a = 90°, b = 97.916(8)°, c = 90°). The closo-cluster B 10 Br 10 2± has a bi...

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“…B 12 Cl 12 had previously been identified by 11 B NMR spectroscopy and mass spectrometry as a by-product of the thermal disproportionation of B 2 Cl 4 . [19] A single-crystal X-ray diffraction study on a blue cubic crystal obtained from a reaction designed to give K[B 12 Cl 12 ] resulted in the structure determination of neutral B 12 Cl 12 ( Figure 3). The B 12 Cl 12 molecules are packed in a cubic closed-packing in the lattice ( Supporting Information, Figure S13).…”

mentioning

confidence: 99%

Oxidation of closo‐[B₁₂Cl₁₂]²⁻ to the Radical Anion [B₁₂Cl₁₂]^.− and to Neutral B₁₂Cl₁₂

et al. 2010

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Compounds containing boron atoms as spin carriers have recently received attention.[1] The icosahedral closo-dodecaborate ion [B 12 H 12 ] 2À is the archetypal boron cluster, and thus of special interest. Whereas the parent cluster [B 12 [3]Alkoxy-substituted ions [B 12 (OR) 12 ] 2À are oxidized at an even lower potential and even neutral B 12 (OR) 12 could be prepared.[4] Very recently, the perhydroxylated radical [B 12 (OH) 12 ]C À has been prepared and structurally characterized.[5] Smaller perhalogenated polyborane cluster radical anions [B n X n ]C À (X = H, Cl, Br, I; n = 6, 8-10), which are derived by one-electron oxidation from the corresponding closo clusters have been prepared and characterized by chemical and electrochemical methods. [6] Halogen substitution and an increasing cluster size significantly increase the resistance to oxidation and consequently the perhalogenated dodecaborates [B 12 X 12 ] 2À (X = halogen) are much more difficult to oxidize. Oxidation of dodecaborates [B 12 X 12 ] 2À (X = H, F, Cl, Br) to give the corresponding radical anions [B 12 X 12 ]C À has been investigated theoretically [7] and by electrochemical methods.[ [9] whilst in earlier electrochemical investigations, the derivatives containing heavier halogens (X = Cl, Br) did not have a well-defined oxidation wave in acetonitrile. [2a, 11] In a recent review, Kaim et al. stated that "Although the oxidation of [B 12 X 12 ] 2À

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2N framework electron clusters: diamagnetic polyhedral boron chlorides, BnCln (n = 8-12), from the thermal disproportionation of diboron tetrachloride

Cited by 30 publications

References 7 publications

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B₈Cl₈, the Radical Anion hypercloso‐[B₈Cl₈]^.− and the Dianion closo‐[B₈Cl₈]²⁻

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B₈Cl₈, the Radical Anion hypercloso‐[B₈Cl₈]^.− and the Dianion closo‐[B₈Cl₈]²⁻

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Oxidation of closo‐[B₁₂Cl₁₂]²⁻ to the Radical Anion [B₁₂Cl₁₂]^.− and to Neutral B₁₂Cl₁₂

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2N framework electron clusters: diamagnetic polyhedral boron chlorides, BnCln (n = 8-12), from the thermal disproportionation of diboron tetrachloride

Cited by 30 publications

References 7 publications

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B8Cl8, the Radical Anion hypercloso‐[B8Cl8].− and the Dianion closo‐[B8Cl8]2−

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B8Cl8, the Radical Anion hypercloso‐[B8Cl8].− and the Dianion closo‐[B8Cl8]2−

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaboratecloso-[B10X10]2- undhypercloso-[B10X10]· - (X = Cl, Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Oxidation of closo‐[B12Cl12]2− to the Radical Anion [B12Cl12].− and to Neutral B12Cl12

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Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B₈Cl₈, the Radical Anion hypercloso‐[B₈Cl₈]^.− and the Dianion closo‐[B₈Cl₈]²⁻

Synthesis and Properties of the Octaboron Cluster Series hypercloso‐B₈Cl₈, the Radical Anion hypercloso‐[B₈Cl₈]^.− and the Dianion closo‐[B₈Cl₈]²⁻

Oxidation of closo‐[B₁₂Cl₁₂]²⁻ to the Radical Anion [B₁₂Cl₁₂]^.− and to Neutral B₁₂Cl₁₂