Dettenrieder Nicole, Schädle Christoph, Maichle-Mössmer Cäcilia, Anwander Reiner
Institute of Inorganic Chemistry, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Dalton Trans. 2014 Nov 14;43(42):15760-70. doi: 10.1039/c4dt02155j.
Treatment of boryllithium (THF)2Li[B(NDippCH)2] (Dipp = 2,6-diisopropylphenyl) with various amounts of AlMe3 or GaMe3 leads to the formation of inter group 13 compounds. Equimolar reactions result in ate complexes of the type (THF)nLi(Me3M)[B(NDippCH)2] (M = Al, Ga) with discrete (n = 2, 3) or eight-membered ring structures (n = 1). We reported previously that use of excessive amounts of group 13 metal methyl compounds can result in four-coordinate THF-adducts (THF)(Me2M)[B(NDippCH)2] or unsolvated complexes {(Me2M)[B(NDippCH)2]}x (M = Al, x = 2; M = Ga, x = 1) via separation of LiMMe4. Polymeric [(THF)Li(Et3Al){B(NDippCH)2}]n is formed when boryllithium is reacted with an equimolar amount of AlEt3. The discrete THF-adduct (THF)Et2Al[B(NDippCH)2] can be isolated when using a boryllithium/AlEt3 ratio of 1 : 5. The reaction of THF-adduct (THF)Me2Ga[B(NDippCH)2] with La(AlMe4)3 affords the heterogallate complex La[(Me3Ga){B(NDippCH)2}]3, according to a donor-assisted tetramethylaluminate/alkylgallate exchange. The obtained complexes feature rare examples of crystallographically characterized non-cluster compounds with unsupported B-Al and B-Ga contacts.
用不同量的三甲基铝或三甲基镓处理硼锂化合物(四氢呋喃)₂Li[B(NDippCH)₂] (Dipp = 2,6 - 二异丙基苯基)会生成第13族元素间化合物。等摩尔反应生成(四氢呋喃)ₙLi(Me₃M)[B(NDippCH)₂]类型的酸根配合物(M = Al、Ga)，具有离散结构(n = 2, 3)或八元环结构(n = 1)。我们之前报道过，使用过量的第13族金属甲基化合物可通过分离LiMMe₄生成四配位的四氢呋喃加合物(四氢呋喃)(Me₂M)[B(NDippCH)₂]或无溶剂配合物{(Me₂M)[B(NDippCH)₂]}ₓ (M = Al, x = 2; M = Ga, x = 1)。当硼锂化合物与等摩尔量的三乙基铝反应时，会形成聚合物[(四氢呋喃)Li(Et₃Al){B(NDippCH)₂}]ₙ。当硼锂化合物与三乙基铝的比例为1∶5时，可以分离出离散的四氢呋喃加合物(四氢呋喃)Et₂Al[B(NDippCH)₂]。根据供体辅助的四甲基铝酸盐/烷基镓酸盐交换反应，四氢呋喃加合物(四氢呋喃)Me₂Ga[B(NDippCH)₂]与La(AlMe₄)₃反应生成杂镓酸盐配合物La[(Me₃Ga){B(NDippCH)₂}]₃。所得到的配合物是具有晶体学表征的非簇状化合物的罕见实例，其中含有未配位的B - Al和B - Ga接触。
