Chlorinated polyhedral selenaboranes revisited by joint experimental/computational efforts: the formation of closo-1-SeB9Cl9 and the crystal structure of closo-SeB11Cl11

Keller, Willi; Hofmann, Matthias; Wadepohl, Hubert; Enders, Markus; Fanfrlík, Jindřich; Hnyk, Drahomír

doi:10.1039/d3dt02987e

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“…Solid-state stereochemistry of heteroboranes has recently relied on the formation of special kinds of noncovalent interactions such as chalcogen bonding, [1][2][3] pnictogen bonding [4] and halogen bonding. [5] These kinds of interactions arise from the σhole concept, which has recently received considerable attention in boron-cluster chemistry.…”

Section: Introductionmentioning

confidence: 99%

Beyond the Limits of Perbromo‐Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

Keller,

Fanfrlík,

Hnyk

2024

Eur J Inorg Chem

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Octahedral closo‐1,2‐Pn2B4Br4 (Pn = P, As) molecules react with tetrahydrothiophene (THT), regarded as a soft base, much slower than with tetrahydrofuran (THF), considered a hard base. Namely, the reaction begins with only Pn = P at temperatures above 140 °C; 4‐Br(CH2)4S‐closo‐1,2‐P2B4Br3 has been detected as the first product resulting in the cleavage and insertion of a thiobutylate group into the B‐Br bond. Unlike in the reaction with THF, the addition of a second THT moiety has not been observed. Conversely, also starting from 140 °C, conjuncto‐3,3’‐(Pn2B4Br3)2 has been found as the final product of the reaction, which indicates the presence of 3‐Br(CH2)4S‐closo‐1,2‐P2B4Br3 as another intermediate during the conversion. A computational examination has revealed that it occurs through a pentagonal pyramidal stationary point as an additional intermediate, the latter of which serves as the crucial structural assembly for the thermal conversion that produces the conjuncto motif. Computations of the energy balance and 11B and 31P NMR chemical shifts are in agreement with experimental observations. This reaction is made possible by the presence of σ‐holes on the bromine atoms. In addition, the presence of the σ‐holes on the pnictogens has enabled ESI‐MS to detect various anions appearing during earlier and current syntheses.

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Section: Introductionmentioning

confidence: 99%

Beyond the Limits of Perbromo‐Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

Keller,

Fanfrlík,

Hnyk

2024

Eur J Inorg Chem

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Chlorinated polyhedral selenaboranes revisited by joint experimental/computational efforts: the formation of closo-1-SeB₉Cl₉ and the crystal structure of closo-SeB₁₁Cl₁₁

Abstract: The newly generated closo-1-SeB9Cl9 and the crystal structure of closo-SeB11Cl11 were investigated, the latter due to the presence of a σ-hole on Se, thus forming a strong chalcogen bond.

Cited by 1 publication

References 40 publications

Beyond the Limits of Perbromo‐Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

Beyond the Limits of Perbromo‐Substituted Octahedral Pnictogenaboranes: A Spectroscopic and Computational Study

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