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Influence of N-Substitution on the Oxidation of 2-Pyridylmethylamines with Bis(trimethylsilyl)amides of Iron(III) : Synthesis of Heteroleptic Iron(II) 2-Pyridylmethylamides

Title data

Malassa, Astrid ; Schulze, Benjamin ; Stein-Schaller, Brigitte ; Görls, Helmar ; Weber, Birgit ; Westerhausen, Matthias:
Influence of N-Substitution on the Oxidation of 2-Pyridylmethylamines with Bis(trimethylsilyl)amides of Iron(III) : Synthesis of Heteroleptic Iron(II) 2-Pyridylmethylamides.
In: European Journal of Inorganic Chemistry. Vol. 2011 (2011) Issue 10 . - pp. 1584-1592.
ISSN 1099-0682
DOI: https://doi.org/10.1002/ejic.201001166

Abstract in another language

The reaction of (thf)Fe[N(SiMe3)2]2Cl with (2-pyridylmethyl)(diphenylphosphanyl)amine (1) in hot tetrahydrofuran (THF) yields dinuclear [(ClFe)2{μ-N(SiMe3)2}{Ph2P(NCH2Py)2}] (2) and [ClFe{Ph2P(O)-NCH2Py}]2 (3) with the oxygen atom stemming from THF degradation. The formation of 2 requires a P–N bond cleavage and reformation leading to the tetradendate diphenyl-bis(2-pyridylmethylamido)phosphonium ion. If this reaction of (thf)Fe[N(SiMe3)2]2Cl with 1 is performed at room temperature, no P–N bond cleavage is observed. Instead of that, ether degradation occurs yielding [Fe4(μ4-O)(μ2-Cl)2(Ph2P-NCH2Py)4] (4) with a central oxygen-centered iron tetrahedron as well as complex 3. Recrystallization of 3 from dichloromethane leads to addition of HCl and to the formation of [FeCl2·{Ph2P(O)-N(H)-CH2Py}] (5). The phosphonium ion of 2 is isoelectronic to the corresponding diphenyl-bis(2-pyridylmethylamino)silane (6). Lithiation of 6 followed by a metathetical reaction with (thf)2FeCl2 yields the trinuclear complex [Fe3Cl2{Ph2Si(NCH2Py)2}2] (7) with antiferromagnetic interactions.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Result of work at the UBT: No
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 27 Jul 2017 11:54
Last Modified: 27 Jul 2017 11:54
URI: https://eref.uni-bayreuth.de/id/eprint/38832