Treatment of β-diketiminato (BDI = HC{C(CH₃)Ndipp)}₂ where dipp = 2,6-iPr₂C₆H₃) magnesium butyl [(BDI)MgBu] (I) and calcium hexamethyldisilazide [(BDI)Ca{N(SiMe₃)₂}] (II) complexes with equimolar quantities of diphenylphosphine–borane, Ph₂PH·BH₃, results in the formation of the respective alkaline earth (Ae) phosphidoborane derivatives [(BDI)Mg(Ph₂PBH₃)]₂ (6a) and [(BDI)Ca(Ph₂PBH₃)] (7a). Although satisfactory single crystals of 7a could not be obtained, 6a was crystallographically characterized and both compounds display similar NMR spectra. The dimeric Ae-hydride complexes [(BDI)AeH]₂ (IIIa, Ae = Mg; IIIb, Ae = Ca) react with substoichiometric quantities of Ph₂PH·BH₃, allowing the crystallization of the dimeric Mg and trimeric Ca phosphidoborane species [(BDI)Mg(H)(H₃BPPh₂)Mg(BDI)] (8) and [{(BDI)Ca}₃(H)(H₃BPPh₂)₂] (9). In the absence of coordinating Lewis bases, compounds 6a, 7a, 8, and 9 display dynamic solution-state behavior (in benzene and toluene), while addition of THF furnishes the monomeric adducts [(BDI)Mg(H₃BPPh₂)·THF] (6b) and [(BDI)Ca(H₃BPPh₂)·THF] (7b). Addition of Ph₂PH·BH₃ to compound 6a results in BH₃ transfer to eliminate Ph₂PH and generate the phosphinodiboronate complex [(BDI)Mg{(H₃B)₂PPh₂}]₂ (10) in preference to dehydrocoupling of the phosphidoborane and phosphine–borane reagents.

中文翻译：

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二苯基膦-硼烷的碱土衍生物

β-二酮亚胺基（BDI = HC {C（CH ₃）Ndipp）} _2的处理，其中dipp = 2,6- i Pr ₂ C ₆ H ₃）丁基镁[（BDI）MgBu]（I）和六甲基二硅叠氮化钙[[ BDI）Ca {N（SiMe ₃）₂ }]（II）与等摩尔量的二苯基膦-硼烷Ph ₂ PH·BH _3的配合物，导致形成相应的碱土金属（Ae）磷硼烷衍生物[（BDI）Mg （Ph ₂ PBH ₃）] ₂（6a）和[（BDI）Ca（Ph ₂ PBH ₃）]（7a）。尽管无法获得令人满意的7a单晶，但对6a进行了晶体学表征，两种化合物均显示出相似的NMR光谱。二聚Ae氢化物络合物[（BDI）AeH] ₂（IIIa，Ae = Mg; IIIb，Ae = Ca）与亚化学计量的Ph ₂ PH·BH _3反应，使Mg和三聚Ca磷硼烷物种结晶[（BDI）Mg（H）（H ₃ BPPh ₂）Mg（BDI）]（8）和[{（BDI）Ca} ₃（H）（H ₃ BPPh ₂）₂ ]（9）。在没有配位的路易斯碱的情况下，化合物6a，7a，8和9表现出动态的溶液状态行为（在苯和甲苯中），而添加THF则提供了单体加合物[（BDI）Mg（H ₃ BPPh ₂）· THF]（6b）和[（BDI）Ca（H ₃ BPPh ₂）·THF]（7b）。在化合物6a中添加Ph ₂ PH·BH ₃导致BH ₃转移以消除Ph ₂ PH并生成次膦酸二硼酸酯络合物[（BDI）Mg {（H ₃ B）₂PPh ₂ }] ₂（10）优先于磷硼烷和膦硼烷试剂的脱氢偶联。