Alkaline-Earth Derivatives of Diphenylphosphine-Borane
Alkaline-Earth Derivatives of Diphenylphosphine-Borane
复制标题
二苯基膦硼烷的碱土衍生物
DOI：
10.1021/acs.organomet.0c00008
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发表时间：
2020
期刊：
影响因子：
2.8
通讯作者：
Morris L
中科院分区：
文献类型：
--
作者：
Morris L
Treatment of β-diketiminato (BDI = HC{C(CH3)Ndipp)}2where 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 of7acould not be obtained,6awas 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, compounds6a,7a,8, and9display 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·BH3to compound6aresults in BH3transfer 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.
