Abstract
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 add...
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