Alkaline-Earth Derivatives of Diphenylphosphine–Borane
| Autor: | Michael S. Hill, Ian Manners, Louis J. Morris, Brian O. Patrick, Mary F. Mahon |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
Alkaline earth metal
Diphenylphosphine 010405 organic chemistry Magnesium Organic Chemistry chemistry.chemical_element Borane 010402 general chemistry 01 natural sciences Medicinal chemistry Toluene 0104 chemical sciences Inorganic Chemistry NMR spectra database chemistry.chemical_compound chemistry Lewis acids and bases Physical and Theoretical Chemistry Benzene |
| Zdroj: | Morris, L J, Hill, M S, Mahon, M F, Manners, I & Patrick, B O 2020, ' Alkaline-Earth Derivatives of Diphenylphosphine-Borane ', Organometallics, vol. 39, no. 23, pp. 4195-4207 . https://doi.org/10.1021/acs.organomet.0c00008 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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