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Reactions of Organic Azides with Half‐sandwich Complexes of Iridium: Preparation of Mono‐ and Bis(imine) Derivatives
Author(s) -
Albertin Gabriele,
Antoniutti Stefano,
Castro Jesús,
Sibilla Francesca
Publication year - 2019
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.201800516
Subject(s) - imine , chemistry , azide , iridium , amine gas treating , medicinal chemistry , crystal structure , stereochemistry , catalysis , crystallography , organic chemistry
Imine complexes [IrCl(η 5 ‐C 5 Me 5 ){κ 1 ‐NH=C(H)Ar}{P(O R ) 3 }]BPh 4 ( 1 , 2 ) (Ar = C 6 H 5 , 4‐CH 3 C 6 H 4 ; R = Me, Et) were prepared by allowing chloro complexes [IrCl 2 (η 5 ‐C 5 Me 5 ){P(OR) 3 }] to react with benzyl azides ArCH 2 N 3 . Bis(imine) complexes [Ir(η 5 ‐C 5 Me 5 ){κ 1 ‐NH=C(H)Ar} 2 {P(O R ) 3 }](BPh 4 ) 2 ( 3 , 4 ) were also prepared by reacting [IrCl 2 (η 5 ‐C 5 Me 5 ){P(O R ) 3 }] first with AgOTf and then with benzyl azide. Depending on the experimental conditions, treatment of the dinuclear complex [IrCl 2 (η 5 ‐C 5 Me 5 )] 2 with benzyl azide yielded mono‐ [IrCl 2 (η 5 ‐C 5 Me 5 ){κ 1 ‐NH=C(H)Ar}] ( 5 ) and bis‐[IrCl(η 5 ‐C 5 Me 5 ){κ 1 ‐NH=C(H)Ar} 2 ]BPh 4 ( 6 ) imine derivatives. In contrast, treatment of chloro complexes [IrCl 2 (η 5 ‐C 5 Me 5 ){P(O R ) 3 }] with phenyl azide C 6 H 5 N 3 gave amine derivatives [IrCl(η 5 ‐C 5 Me 5 )(C 6 H 5 NH 2 ){P(O R ) 3 }]BPh 4 ( 7 , 8 ). The complexes were characterized spectroscopically (IR, NMR) and by X‐ray crystal structure determination of [IrCl(η 5 ‐C 5 Me 5 ){κ 1 ‐NH=C(H)C 6 H 4 ‐4‐CH 3 }{P(OEt) 3 }]BPh 4 ( 2b ).