Efficient Hydride and Pyrazolyl Redistribution upon Thermolysis of a Calcium Complex Containing Dihydrobis(pyrazolyl)borate Ligands

Thermolysis of CaBp2(THF)2 (THF = tetrahydrofuran) at 190–200 °C and 0.05 Torr leads to a redistribution reaction to afford CaTp2 (90%) and CaTp(BH4) (84%). Treatment of CaTp(BH4) with THF affords CaTp(BH4)(THF)2 and [CaTp(BH4)(THF)]4, both of which were structurally characterized. Methanolysis or ethanolysis/hydrolysis of the BH4–-containing complexes affords [TpCa(HOMe)2(μ4-B(OMe)4)Ca(HOMe)2Tp][B(OMe)4] and [{TpCa}3{μ6-B(OB(OEt)3)3]·EtOH.在190~200 ℃、0.05 Torr（压强单位托）条件下对CaBp₂(THF)₂（THF即四氢呋喃（tetrahydrofuran））进行热解，可发生重分配反应，生成CaTp₂（产率90%）与CaTp(BH₄)（产率84%）。用THF处理CaTp(BH₄)，可得到CaTp(BH₄)(THF)₂与[CaTp(BH₄)(THF)]₄，两种产物均完成了结构表征。对含BH₄⁻的配合物进行甲醇解或乙醇解/水解，可得到[TpCa(HOMe)₂(μ₄-B(OMe)₄)Ca(HOMe)₂Tp][B(OMe)₄]与[{TpCa}₃{μ₆-B(OB(OEt)₃)₃}]·乙醇（EtOH）。