Abstract
The synthesis and structural characterization of new derivatives of [B12H12]2− is of fundamental interest and is expected to allow for extended applications. Herein we report on the synthesis of a series of amidine, amide, urea and isocyanate derivatives based on the amino-closo-dodecaborate anion [B12H11NH3]−. Their structures have been confirmed by spectroscopic methods, and nine crystal structures are presented.
Highlights
The closo-dodecaborate dianion [B12 H12 ]2− (1, Figure 1) is an icosahedral boron cluster with 12 identical B–H vertices, and it possesses unique properties such as spherical electron delocalization and high thermal/chemical stability [1,2,3,4]
Dodecaborate amidines 6 have not been explored yet, and urea derivatives 7 were unknown until we recently found that the reaction of 2 with dialkylcarbamoyl chlorides ClC(O)NMe2 or ClC(O)NEt2 affords the corresponding {B12 }-substituted N,N-dialkyl ureas [39]
Amidine derivatives based on the {B12 } cluster have not been reported before, and in the Synthesis of {B12}-based
Summary
The closo-dodecaborate dianion [B12 H12 ]2− (1, Figure 1) is an icosahedral boron cluster with 12 identical B–H vertices, and it possesses unique properties such as spherical electron delocalization and high thermal/chemical stability [1,2,3,4] It is considered a 3D analogue of benzene, and applications of [B12 H12 ]2− as well as its derivatives have been found in many fields, such as weakly coordinating anions [5,6,7,8,9,10,11,12,13,14], medicinal chemistry [15,16,17], catalysis [18,19], ligand design [20,21,22] and supramolecular chemistry [23,24,25,26,27]. We present: (1) the synthesis of three new {B12 }-based amidines 6 with two crystal structures; (2) six crystal structures of {B12 }-based
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