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Steering Of Configuration By (2-Phosphanyl)phenolato Ligands In Trimethylphosphane Iron Complexes

H. Klein, Markus Frey, Shizhen Mao
Published 2005 · Chemistry

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(Diphenylphosphanyl)phenols C6H3(1-OH)(2-PPh2)(4-R1)(6-R2), abbreviated as (P∧OH), oxidatively add to Fe(PMe3)4 affording hydridoiron(II) compounds fac-FeH(P∧O)(PMe3)3 (1: R1=R2=H; 2: R1=Me, R2=H; 3: R1=OMe, R2=H; 4: R1=Me, R2=CMe3; 5: R1=R2=CMe3) with high stereoselectivity. (2-diphenylphosphanyl)thiophenol (P∧SH) reacts accordingly forming fac-FeH(P∧S)(PMe3)3 (9). Complete assignment of 1H, 13C, and 31P signals is achieved by 2D heteronuclear shift correlations. 4,6-Di-tert-butyl-(2-diphenylphosphanyl)phenol reacts with FeI(Me)(PMe3)4 to form FeI(P∧O)(PMe3)2 (6). 4, 5 and 9 under 1 bar of CO are converted to monocarbonyl derivatives FeH(P∧X)(CO)(PMe3)2 (7, 8: X = O; 10: X = S) which in solution form mixtures of two isomers A and B. 4 and 5 react with their parent phosphanylphenols, respectively, to give diamagnetic complexes Fe(P∧O)2(PMe3) (11, 12) which dissociate trimethylphosphane to give paramagnetic compounds Fe(P∧O)2. The same phosphanylphenols react with FeCl3 to afford racemic mixtures of complexes Fe(P∧O)3 (13, 14). Structural data were also obtained from single crystals of compounds 1, 5, and 11.
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