Thermal Dehydrogenation of Base-Stabilized B2H5(+) Complexes and Its Role in C-H Borylation.
Thermal Dehydrogenation of Base-Stabilized B2H5(+) Complexes and Its Role in C-H Borylation.
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DOI：
10.1002/anie.201507647
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发表时间：
2015-11-02
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影响因子：
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通讯作者：
Prokofjevs A
中科院分区：
文献类型：
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作者：
Prokofjevs A
热诱导h桥阳离子L2B2H5+ （L = Lewis碱）脱氢被认为是叔胺硼烷分子内C-H硼化反应的关键步骤。从L2B2H5+中损失H2产生高活性阳离子L2B2H3+，在其sp2-sp3二硼烷(4)形式下，然后经历分子内C-H插入与B-B键切割，或捕获BH3产生L2B3H6+。通过L2B2H5+ HB(C6F5)3−歧化形成LBH2C6F5配合物，说明了反离子稳定性对反应结果的影响。
Thermally induced dehydrogenation of the H-bridged cation L2B2H5+ (L = Lewis base) is proposed to be the key step in the intramolecular C–H borylation of tertiary amine boranes activated with catalytic amounts of strong “hydridophiles”. Loss of H2 from L2B2H5+ generates the highly reactive cation L2B2H3+, which in its sp2–sp3 diborane(4) form then undergoes either an intramolecular C–H insertion with B–B bond cleavage, or captures BH3 producing L2B3H6+. The effect of the counterion stability on the outcome of the reaction is illustrated by formation of LBH2C6F5 complexes through disproportionation of L2B2H5+ HB(C6F5)3−.