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Steering of Configuration by (2‐Phosphanyl)phenolato Ligands in Trimethylphosphane Iron Complexes
Author(s) -
Klein HansFriedrich,
Frey Markus,
Mao Shizhen
Publication year - 2005
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200500021
Subject(s) - chemistry , thiophenol , stereoselectivity , heteronuclear molecule , medicinal chemistry , stereochemistry , phenols , phosphinate , nuclear magnetic resonance spectroscopy , crystallography , organic chemistry , catalysis , fire retardant
(Diphenylphosphanyl)phenols C 6 H 3 (1‐OH)(2‐PPh 2 )(4‐R 1 )(6‐R 2 ), abbreviated as (P ∧ OH), oxidatively add to Fe(PMe 3 ) 4 affording hydridoiron(II) compounds fac ‐FeH(P ∧ O)(PMe 3 ) 3 ( 1 : R 1 =R 2 =H; 2 : R 1 =Me, R 2 =H; 3 : R 1 =OMe, R 2 =H; 4 : R 1 =Me, R 2 =CMe 3 ; 5 : R 1 =R 2 =CMe 3 ) with high stereoselectivity. (2‐diphenylphosphanyl)thiophenol (P ∧ SH) reacts accordingly forming fac ‐FeH(P ∧ S)(PMe 3 ) 3 ( 9 ). Complete assignment of 1 H, 13 C, and 31 P signals is achieved by 2D heteronuclear shift correlations. 4,6‐Di‐ tert ‐butyl‐(2‐diphenylphosphanyl)phenol reacts with FeI(Me)(PMe 3 ) 4 to form FeI(P ∧ O)(PMe 3 ) 2 ( 6 ). 4 , 5 and 9 under 1 bar of CO are converted to monocarbonyl derivatives FeH(P ∧ X)(CO)(PMe 3 ) 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 (PMe 3 ) ( 11 , 12 ) which dissociate trimethylphosphane to give paramagnetic compounds Fe(P ∧ O) 2 . The same phosphanylphenols react with FeCl 3 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 .