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CO-migration in the ligand substitution process of the chelating diphosphite diiron complex (mu-pdt) Fe(CO)(3) Fe(CO){(EtO)(2)PN(Me)P(OEt}(2)
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2008 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 47, no 15, 6948-6955 p.Article in journal (Refereed) Published
Abstract [en]

Selective synthetic routes to isomeric diiron dithiolate complexes containing the (EtO)(2)PN(Me)P(OEt)(2) (PNP) ligand in an unsymmetrical chelating role, for example, (mu-pdt)[Fe(CO)(3)][Fe(CO)(kappa(2)-PNP)] (3) and as a symmetrically bridging ligand in (mu-pdt)(mu-PNP)[Fe(CO)(2)](2) (4), have been developed. 3 was converted to 4 in 75% yield after extensive reflux in toluene. The reactions of 3 with PMe3 and P(OEt)(3) afforded bis-monodentate P-donor complexes (mu-pdt)[Fe(CO)(2)PR3][Fe(CO)(2)(PNP)] (PR3 = PMe3 5; P(OEt)(3), 7), respectively, which are formed via an associative PMe3 coordination reaction followed by an intramolecular CO-migration process from the Fe(CO)3 to the Fe(CO)(PNP) unit with concomitant opening of the Fe-PNP chelate ring. The PNP-monodentate complexes 5 and 7 were converted to a trisubstituted diiron complex (mu-pdt)(mu-PNP)[Fe(CO)PR3][Fe(CO)(2)] (PR3 = PMe3, 6; P(OEt)(3), 8) on release of 1 equiv CO when refluxing in toluene. Variable-temperature P-31 NMR spectra show that trisubstituted diiron complexes each exist as two configuration isomers in solution. All diiron dithiolate complexes obtained were characterized by MS, IR, NMR spectroscopy, elemental analysis, and X-ray diffraction studies.

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2008. Vol. 47, no 15, 6948-6955 p.
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URN: urn:nbn:se:kth:diva-17730DOI: 10.1021/ic800525nISI: 000257991000045Scopus ID: 2-s2.0-49649099746OAI: oai:DiVA.org:kth-17730DiVA: diva2:335775
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QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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