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Mono‐ and Dinuclear High‐Spin Half‐Sandwich Manganese( II ) Complexes Containing Acetylide and TMEDA Ligands
Author(s) -
Kheradmandan Sohrab,
Fox Thomas,
Schmalle Helmut W.,
Venkatesan Koushik,
Berke Heinz
Publication year - 2004
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.200400006
Subject(s) - chemistry , acetylide , tetramethylethylenediamine , manganese , raman spectroscopy , crystallography , medicinal chemistry , stereochemistry , organic chemistry , physics , optics
The d 5 high‐spin Mn II half‐sandwich complexes [Mn(C≡CR)(MeC 5 H 4 )(tmeda)] (R = SiMe 3 2 ; Ph 3 ; t Bu 4 ; C≡CSiMe 3 5 ; C≡CPh 6 ; tmeda = N , N , N′ , N′ ‐tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC 5 H 4 ) 2 (tmeda)] ( 1 ) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C−C≡CSiMe 3 ) 2 (tmeda)] 2 ( 7 ) and [Mn 2 (MeCp) 2 (μ 1 ‐ t BuC≡C) 2 (μ 1 ‐tmeda)] ( 8 ), which contain Mn−Mn bonds, were synthesized by treating 1 with an excess of HC≡C−C≡CSiMe 3 or HC≡C t Bu, respectively. Dinuclear complexes of the type [(MeC 5 H 4 )(tmeda)MnC≡C− X−C≡CMn(tmeda)(C 5 H 4 Me)] [X = 1,3‐C 6 H 4 9 ; 1,4‐C 6 H 4 10 ; 4,4′‐(C 6 H 4 ) 2 11 ] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3‐C 6 H 4 (C≡CSnMe 3 ) 2 , 1,4‐C 6 H 4 (C≡CSnMe 3 ) 2 and 4,4′‐(C 6 H 4 ) 2 (C≡CSnMe 3 ) 2 in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono‐ and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X‐ray diffraction studies have been performed on complexes 3 and 5 − 11 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)