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Synthesis, Structure, and Reactivity of Chiral Rhenium Amido Complexes of the Formula (η 5 ‐C 5 H 5 )Re(NO)(PPh 3 )(NRR')
Author(s) -
Dewey Michael A.,
Andrew Knight D.,
Arif Atta,
Gladysz J. A.
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250410
Subject(s) - chemistry , rhenium , amine gas treating , crystal structure , reactivity (psychology) , nitrogen atom , stereochemistry , medicinal chemistry , nuclear magnetic resonance spectroscopy , alkylation , x ray crystallography , crystallography , catalysis , ring (chemistry) , organic chemistry , medicine , physics , alternative medicine , pathology , diffraction , optics
Reactions of primary and secondary amine complexes [(η 5 ‐C 5 H 5 )Re(NO)(PPh 3 )(NHRR')] + TfO − [ 2 ; R/R' = H/H ( a ), H/CH 3 ( b ), H/C 6 H 5 ( d ), CH 3 /CH 3 ( f ), CH 2 CH 2 CH 2 CH 2 ( h )] with n BuLi give amido complexes (η 5 ‐C 5 H 5 )Re(NO)(PPh 3 )(NRR') ( 1 ) in quantitative NMR yields. Although 1 d can be isolated in pure form, 1 f is converted upon workup into a dimeric bridging bis(amido) complex, cis ‐[(η 5 ‐C 5 H 5 )Re(NO){μ‐N(CH 3 ) 2 }] 2 . The crystal structure of 1 d exhibits a pyramidal amido nitrogen atom. The diastereotopic methyl groups in 1 f readily exchange, as assayed by variable‐temperature NMR. Complexes 1 a, f react with TfOH to regenerate 2a, f , and with TfOR” to give the corresponding alkylated amine complexes. The basicities and nucleophilicities of the amido nitrogen atoms are shown to be greater than those of organic amines.