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Reactivity of 2‐mercaptopyridines with Iridium(I)‐Tris(pyrazolyl) borate complexes
Author(s) -
GomezBonilla Manuel A.,
SalazarPereda Verónica,
MendozaEspinosa Daniel,
GonzalezMontiel Simplicio,
CastañedaOvando Aracely,
RojasLima Susana,
SandovalChavez Cesar I.,
LopezJímenez Jorge A.
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202001153
Subject(s) - chemistry , deprotonation , iridium , moiety , reactivity (psychology) , molecule , infrared spectroscopy , medicinal chemistry , stereochemistry , benzene , nuclear magnetic resonance spectroscopy , crystallography , catalysis , organic chemistry , ion , medicine , alternative medicine , pathology
Reaction of of the Ir(I) complex [Tp Me2 Ir−(C 2 H 4 ) 2 ] ( 1 ) with a variety of mercaptopyridines produces in good yields the Ir(III)‐metallacycles 2 – 4 with the general formula [Tp Me2 Ir(C 2 H 5 )( k 2 ‐(N,S)‐mercaptopyridine)]. Complexes 2 – 4 are proposed to take place by the initial formation of the 16 electron intermediate [Tp Me2 Ir(CH=CH2)(C2H5)] which then coordinates the nitrogen atom of the mercaptopyridine and promotes the deprotonation of the SH group via the elimination of an ethylene molecule. Heating of complex [Tp Me2 Ir( η 4 ‐CH 2 =C(Me)C(Me)=CH 2 )]] ( 5 ) at 100 °C with the substituted mercaptopyridines results in the formation of the Ir(III) complexes 6 – 8 with the general formula [Tp Me2 Ir(C 6 H 5 )( κ 2 ‐(N,S)‐mercaptopyridine)]. Generation of complexes 6 – 8 is proposed to take place by the initial formation of the [Tp Me2 Ir(C 6 H 5 ) 2 N 2 ] complex which after releasing nitrogen coordinates the mercaptopyridine in a η 1 ‐fashion and favour the SH moiety deprotonation with the release of a benzene molecule. All complexes have been fully characterized by NMR spectroscopy, FT‐IR, elemental analysis and in the case of 2 , 4 , and 8 by X‐ray crystallography. Details of the reaction conditions, characterization and isolation of the products will be discussed.