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Selective White Phosphorus Activation and Functionalization with Inorganic Grignard Reagents
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DOI：10.1039/D6SC01229A.png)
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Abstract
En 中文
We describe the targeted and selective functionalization of white phosphorus (P4) using ‘inorganic Grignard reagents’. Reactions of the Fe-Mg complexes [(DippBDI)Mg(THF)xFp] (Fp = CpFe(CO)2; 1: x = 0; 1 THF: x = 1; DippBDI = 2; 6-diisopropylphenyl-1; 3 diketiminate)) and [(DippBDI)MgFp*] (2; Fp* = Cp*Fe(CO)2) afford the compounds [(DippBDI)Mg(THF)x][Fp(μ-P4)] (3: x = 0; 3 THF: x = 1) and [(DippBDI)Mg][Fp*(μ-P4)] (4) featuring P42- ligands with a ‘butterfly’ structure bridging Fe and Mg. The coordination of the β-diketiminate magnesium cations [(DippBDI)Mg]+ plays a key role in stabilizing these reactive ‘P4-butterfly’ anions through non-covalent Mg–P bonds and dispersion forces. Thermolysis or photolysis of 3-THF and 4 afforded rare tetraphosphacyclopentadienolate complexes 7 and 8. Complex 4 exhibits unmitigated reactivity towards a wide range of main group element electrophiles (iPrNCNiPr; Ph2BCl; Ph3SnCl (Me3Si)3SiCl and Mes2PCl); furnishing rare examples of stable; mixed-substituted tetraphosphanes 9-13 as well as an octaphosphane 14 featuring a Sn2P8 core.
Keywords:
white phosphorus
inorganic Grignard reagents
P4-butterfly complex
tetraphosphacyclopentadienolate
functionalization