Fe(IV) alkylidenes via protonation of Fe(II) vinyl chelates and a comparative Mossbauer spectroscopic study

被引：38

作者：

Lindley, Brian M. ^{[1
]}

Swidan, Ala'aeddeen ^{[1
]}

Lobkovsky, Emil B. ^{[1
]}

Wolczanski, Peter T. ^{[1
]}

Adelhardt, Mario ^{[2
]}

Sutter, Joerg ^{[2
]}

Meyer, Karsten ^{[2
]}

机构：

[1] Cornell Univ, Baker Lab, Dept Chem & Biol Chem, Ithaca, NY 14850 USA

[2] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

来源：

CHEMICAL SCIENCE | 2015年 / 6卷 / 08期

基金：

美国国家科学基金会;

关键词：

C-H ACTIVATION; CARBENE COMPLEXES; OLEFIN-METATHESIS; SPECTRAL CHARACTERIZATION; IRON; GENERATION; DERIVATIVES; (ETA-5-CYCLOPENTADIENYL)DICARBONYLIRON; TRIMETHYLPHOSPHINE; MOLYBDENUM;

D O I：

10.1039/c5sc01268f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of cis-Me2Fe(PMe3)(4) with di-1,2-(E-2-(pyridin-2-yl)vinyl)benzene ((bdvp)H-2), a tetradentate ligand precursor, afforded (bdvp)Fe(PMe3)(2) (1-PMe3) and 2 equiv. CH4, via C-H bond activation. Similar treatments with tridentate ligand precursors PhCH=NCH2(E-CH=CHPh) ((pipp)H-2) and PhCH=N(2-CCMe-Ph) ((pipa)H) under dinitrogen provided trans-(pipp)Fe(PMe3)(2)N-2 (2) and trans-(pipvd) Fe(PMe3)(2)N-2 (3), respectively; the latter via one C-H bond activation, and a subsequent insertion of the alkyne into the remaining Fe-Me bond. All three Fe(II) vinyl species were protonated with H[BAr4F] to form the corresponding Fe(IV) alkylidene cations, [(bavp)Fe(PMe3)(2)][BAr4F] (4-PMe3), [(piap)Fe(PMe3)(3)]-[BAr4F] (5), and [(pipad) Fe(PMe3)(3)][BAr4F] (6). Mossbauer spectroscopic measurements on the formally Fe(II) and Fe(IV) derivatives revealed isomer shifts within 0.1 mm s(-1), reflecting the similarity in their bond distances.

引用

页码：4730 / 4736

页数：7

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