Synthesis and reactivity of silyl iron hydride via Si H bond activation

The preligand pyridine-2-amino(methyl)-dimethylsilane (1) was used to synthesize silyl iron hydride. Iron(II) hydride FeH(N(κN-C5H4N)Me(SiMe2))(PMe3)3 (2) was obtained through the reaction of 1 and Fe(PMe3)4 via the activation of one Si-H bond and the coordination of nitrogen atom of pyridine. The s...

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Published inInorganica Chimica Acta Vol. 455; pp. 112 - 117
Main Authors Shi, Yaomin, Li, Xiaoyan, Zheng, Tingting, Xue, Benjing, Zhang, Shumiao, Sun, Hongjian, Fuhr, Olaf, Fenske, Dieter
Format Journal Article
LanguageEnglish
Published Amsterdam Elsevier Science Ltd 30.01.2017
Subjects
Acetylacetone
Activation
Atoms & subatomic particles
Chemical bonds
Chemical reactions
Chemical synthesis
Hydrides
Hydrogen bonds
Insertion
Iron
Molecular chains
Molecular structure
Nitrogen
Single crystals
Substitution reactions
X-ray diffraction
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Summary:The preligand pyridine-2-amino(methyl)-dimethylsilane (1) was used to synthesize silyl iron hydride. Iron(II) hydride FeH(N(κN-C5H4N)Me(SiMe2))(PMe3)3 (2) was obtained through the reaction of 1 and Fe(PMe3)4 via the activation of one Si-H bond and the coordination of nitrogen atom of pyridine. The substitution reaction of complex 2 with haloalkane (CH3I and EtBr) delivered complexes FeX(N(κN-C5H4 N)Me(SiMe2))(PMe3)3 (X = I (3); Br (4)). Complex 2 reacting with acetylacetone resulted in the formation of Fe(acac)(N(κN-C5H4N)Me(SiMe2))(PMe3)3 (5). However, the insertion products Fe(η3-OCOH)(N(κN-C5H4N)Me(SiMe2))(PMe3)3 (6) and Fe(η3-Ph-NCOH)(N(κN-C5H4N)Me(SiMe2))(PMe3)3 (7) were formed through the insertion of the unsaturated bonds into Fe-H bond. Complex 6 could also be synthesized through the substitution reaction of 2 with HCOOH. The molecular structures of complexes 2 and 4–7 were determined by single crystal X-ray diffraction.
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2016.10.017