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Nucleophilic Addition of Secondary Phosphines to Cationic Dienyl Tricarbonyliron Complexes: A novel Route to Optically Active Phosphines
Author(s) -
Englert Ulli,
Ganter Beate,
Käser Markus,
Klinkhammer Elke,
Wagner Trixie,
Salzer Albrecht
Publication year - 1996
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19960020511
Subject(s) - optically active , cationic polymerization , chemistry , nucleophile , nucleophilic addition , medicinal chemistry , combinatorial chemistry , organic chemistry , catalysis
Secondary phosphines such as HPPh 2 and to the cationic iron dienyl complex [η 5 ‐(1 R )‐ethylnopadienyl)Fe‐(CO) 3 ] + ( 1 ) by nucleophilic addition. The phosphonium salt initially formed is readily deprotonated to yield an optically active tertiary phosphine [( n 4 ‐(1 R )‐ethylnopadienePPh 2 )Fe(CO) 3 ] ( 2b ). A similar reaction also occurs with [C 6 H 7 Fe‐(CO) 3 ] + ( 3 ) and [C 7 H 9 Fe(CO) 3 ] + ( 4 ) to give [(C 6 H 7 PPh 2 )Fe(CO) 3 ] ( 5 ) and [(C 7 H 9 PPh 2 )Fe(CO) 3 ] ( 6 ) in good yields. The mechanism of formation of these novel phosphines is discussed. Complex 2 b crystallizes in the space group P 2 1 2 1 2 1 (no. 19); 5 crystallizes in the space group P 2 1 / c (no. 14). Like other monodentate optically active phosphines, 2 b is capable of coordinating to transition metal complexes. It forms palladium complexes on reaction with [{μ‐chloro(allyl)palladium} 2 ] as well as with [{μ‐chloro[( N,N ‐dimethylamino‐ kN ‐2‐methyl)phenyl‐ kC ]palladium} 2 ] ( 11 ). The latter reaction product crystallizes in the space group P 3 1 (no. 144).