Bond activation in iron(II) and nickel(II) complexes of polypodal phosphanes

dc.contributor.authorGentschow, Simon-Andreas
dc.contributor.authorKohl, Stephan W.
dc.contributor.authorBauer, Walter
dc.contributor.authorHeinemann, Frank W.
dc.contributor.authorWiedemann, Dennis
dc.contributor.authorGrohmann, Andreas
dc.date.accessioned2016-09-13T12:02:44Z
dc.date.available2016-09-13T12:02:44Z
dc.date.issued2010
dc.description.abstractA 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)]en
dc.identifier.eissn1865-7117
dc.identifier.issn0932-0776
dc.identifier.urihttp://depositonce.tu-berlin.de/handle/11303/5896
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-5489
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.otherbond activationen
dc.subject.otherN/P ligandsen
dc.subject.otherpolypodal ligandsen
dc.subject.otheragostic interactionen
dc.subject.otherironen
dc.subject.othernickelen
dc.titleBond activation in iron(II) and nickel(II) complexes of polypodal phosphanesen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1515/znb-2010-0304
dcterms.bibliographicCitation.issue3
dcterms.bibliographicCitation.journaltitleZeitschrift für Naturforschung : B, a journal of chemical sciencesen
dcterms.bibliographicCitation.originalpublishernameDe Gruyteren
dcterms.bibliographicCitation.originalpublisherplaceBerlinen
dcterms.bibliographicCitation.pageend250
dcterms.bibliographicCitation.pagestart238
dcterms.bibliographicCitation.volume65
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Anorganische Chemie - Festkörper- und Materialchemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Anorganische Chemie - Festkörper- und Materialchemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin
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