TY - JOUR
T1 - Synthesis of LiBC4N4, BC3N3, and related C-N compounds of boron
T2 - New precursors to light element ceramics
AU - Williams, Darrick
AU - Pleune, Brett
AU - Kouvetakis, John
AU - Williams, M. D.
AU - Andersen, R. A.
PY - 2000/8/16
Y1 - 2000/8/16
N2 - The synthesis of a novel framework cyanide with composition LiBC4N4 (1) is described. X-ray powder diffraction as well as 7Li, 11B, and 13C NMR of 1 reveal an ordered structure which consists of two interpenetrating diamond-like networks of BC4 and LiN4 tetrahedra linked by C-N bonds. The structure is simple cubic, symmetry P43m, a = 5476(3) Å. In solution the presence of the B(CN)4 anion has been established for the first time by spectroscopic methods. Molecular B(CN)3 is isolated for the first time as a Lewis acid-base complex with bases such as NMe3 and SiMe3CN, and a single-crystal X-ray structure of B(CN)3NMe3 (3) has been obtained. The novel solid-state cyanide BC3N3 (2) is prepared from the thermal elimination of NCSiMe3 from B(CN)3NCSiMe3 (4). In route to 4, compounds B(CN)2(SMe)NCSiMe3 (5) and B(CN)2(SMe)-NMe3 (6) have also been isolated. A single-crystal X-ray structure of 6 reveals that the compound crystallizes in the monoclinic space group P21/n. The new crystalline solids 2 and 1 (isoelectronic to C) are promising precursors for high-pressure and high-temperature syntheses of novel phases with structures related to Si3N4, diamond, and graphite.
AB - The synthesis of a novel framework cyanide with composition LiBC4N4 (1) is described. X-ray powder diffraction as well as 7Li, 11B, and 13C NMR of 1 reveal an ordered structure which consists of two interpenetrating diamond-like networks of BC4 and LiN4 tetrahedra linked by C-N bonds. The structure is simple cubic, symmetry P43m, a = 5476(3) Å. In solution the presence of the B(CN)4 anion has been established for the first time by spectroscopic methods. Molecular B(CN)3 is isolated for the first time as a Lewis acid-base complex with bases such as NMe3 and SiMe3CN, and a single-crystal X-ray structure of B(CN)3NMe3 (3) has been obtained. The novel solid-state cyanide BC3N3 (2) is prepared from the thermal elimination of NCSiMe3 from B(CN)3NCSiMe3 (4). In route to 4, compounds B(CN)2(SMe)NCSiMe3 (5) and B(CN)2(SMe)-NMe3 (6) have also been isolated. A single-crystal X-ray structure of 6 reveals that the compound crystallizes in the monoclinic space group P21/n. The new crystalline solids 2 and 1 (isoelectronic to C) are promising precursors for high-pressure and high-temperature syntheses of novel phases with structures related to Si3N4, diamond, and graphite.
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U2 - 10.1021/ja0006752
DO - 10.1021/ja0006752
M3 - Article
AN - SCOPUS:0034674977
SN - 0002-7863
VL - 122
SP - 7735
EP - 7741
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 32
ER -