Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-5489
Main Title: Bond activation in iron(II) and nickel(II) complexes of polypodal phosphanes
Author(s): Gentschow, Simon-Andreas
Kohl, Stephan W.
Bauer, Walter
Heinemann, Frank W.
Wiedemann, Dennis
Grohmann, Andreas
Type: Article
Language Code: en
Abstract: A pyridine-derived tetraphosphane ligand (donor set: NP4) has been found to undergo remarkably specific C-P bond cleavage reactions, thereby producing a ligand with an NP3 donor set. The reaction may be reversed under suitable conditions, with regeneration of the original NP4 ligand. In order to investigate the mechanism of this reaction, the NP3 donor ligand C5H3N[CMe(CH2PMe2)2][CMe2(CH2PMe2)] (11) was prepd., and its iron(II) complex 4 generated from Fe(BF4)2·6 H2O, with Me diethylphosphinite (7) as an addnl. monodentate ligand. Ligand 11 has, in addn. to the NP3 donor set, one Me group in close contact with the iron center, reminiscent of an agostic M···H-C interaction. Depending on the stoichiometric amt. of iron(II) salt, a side product 15 is formed, which has a diethylphosphane ligand instead of the phosphinite 7 coordinated to iron(II). While attempts to deprotonate the metal-coordinated Me group in 4 were unsuccessful, the reaction was shown to occur in an alternative complex (18), which is similar to 4 but has a trimethylphosphane ligand instead of the phosphinite 7. The reaction of complex 15 with CO gave two different products, which were both characterized by single-crystal X-ray diffraction. One (19) is the dicarbonyl iron(II) complex of the triphosphane ligand 11, the other (3) is the carbonyl iron(II) complex of the tetraphosphane C5H3N[CMe(CH2PMe2)2]2 (1). This suggests an intermol. mechanism for the C-P bond formation in question. [on SciFinder(R)]
URI: http://depositonce.tu-berlin.de/handle/11303/5896
http://dx.doi.org/10.14279/depositonce-5489
Issue Date: 2010
Date Available: 13-Sep-2016
DDC Class: 540 Chemie
Subject(s): bond activation
N/P ligands
polypodal ligands
agostic interaction
iron
nickel
Creative Commons License: https://creativecommons.org/licenses/by-nc-nd/3.0/
Journal Title: Zeitschrift für Naturforschung : B, a journal of chemical sciences
Publisher: De Gruyter
Publisher Place: Berlin
Volume: 65
Issue: 3
Publisher DOI: 10.1515/znb-2010-0304
Page Start: 238
Page End: 250
EISSN: 1865-7117
ISSN: 0932-0776
Appears in Collections:Technische Universität Berlin » Fakultäten & Zentralinstitute » Fakultät 2 Mathematik und Naturwissenschaften » Institut für Chemie » Fachgebiet Anorganische Chemie - Festkörper- und Materialchemie » Publications

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