Reactions of 6,9-Bis(dimethyl sulfide)- decaborane(14), 6,9-[(CH₃)₂S]₂B₁₀H₁₂:  Mechanistic Considerations

Abstract

The deuterium-labeled 6,9-[(CH3)2S]2-2,4-D2B10H10 is formed regiospecifically from 2,4-D2B10H12 and (CH3)2S. Likewise, the deuterium labels are retained in the same relative locations when 6,9-[(CH3)2S]2-2,4-D2B10H10 is converted to 5-[(CH3)2S]-2,4-D2B10H10, by thermal ligand displacement, and to 5-[(CH3)2S]-9-(Thx)-2,4-D2B10H9 by hydroboration of 2,3-dimethyl-2-butene.

Rearrangements in the Nona‐ and Azanonaborane Clusters

“…At the same time, the second R 1 NH 2 moiety migrates from B 5 to the exo position of B 4 [11]. An analogous migration is described in the literature [8].…”

Rearrangements in the nona-and azanonaborane clusters

“…At the same time, the second R 1 NH 2 moiety migrates from B 5 to the exo position of B 4 [11]. An analogous migration is described in the literature [8]. With a diamond-square-diamond (DSD) rearrangement [14] Depending on the final stereochemistry of the product, the attack of the initial amine (and probably the second and third amine as well), might also take place on atom B 9 ( Fig.…”

“…We have prepared some of these compounds where R = Et, Br, and D, respectively. These compounds can readily be converted via the twostep procedure, with 6,9-(Me 2 S) 2 B 10 H 12 derivatives as intermediates to the corresponding arachnononaborane system [7][8][9]. The labels were chosen because they are stable under the reaction conditions: Neither the bromine atom nor the ethyl group can be removed by Et 3 N [7], and no deuterium exchange has been noted in refluxing the tetradeuterated (Me 2 S)B 9 H 13 with diethylamine in benzene [9].…”

Macropolyhedral boron-containing cluster chemistry. A synthetic approach via the auto-fusion of [6,9-(SMe2)2-arachno-B10H12]

“…It has been demonstrated that there is probably no re-arrangement of the boron atom positions within the skeleton during this process. 24 The crystallographic determination of compound 2 has previously been reported. 23 In this previous report, however, it was only possible to solve the structure as a racemic twin in space group P2 1 2 1 2 1 .…”