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Synthesis, structures and stabilities of thioanisole-functionalised phosphido-borane complexes of the alkali metals
Treatment of the secondary phosphine {(Me3Si) 2CH}PH(C6H4-2-SMe) with BH3¡¤ SMe2 gives the corresponding phosphine-borane {(Me 3Si)2CH}PH(BH3)(C6H 4-2-SMe) (9) as a colourless solid. Deprotonation of 9 with n-BuLi, PhCH2Na or PhCH2K proceeds cleanly to give the corresponding alkali metal complexes [[{(Me3Si)2CH} P(BH3)(C6H4-2-SMe)]ML]n [ML = Li(THF), n = 2 (10); ML = Na(tmeda), n = ? (11); ML = K(pmdeta), n = 2 (12)] as yellow/orange crystalline solids. X-ray crystallography reveals that the phosphido-borane ligands bind the metal centres through their sulfur and phosphorus atoms and through the hydrogen atoms of the BH3 group in each case, leading to dimeric or polymeric structures. Compounds 10-12 are stable towards both heat and ambient light; however, on heating in toluene solution in the presence of 10, traces of free phosphine-borane 9 are slowly converted to the free phosphine {(Me3Si)2CH}PH(C 6H4-2-SMe) (5) with concomitant formation of the corresponding phosphido-bis(borane) complex [{(Me3Si) 2CH}P(BH3)2(C6H4-2-SMe)] Li (14). The Royal Society of Chemistry 2011.
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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI