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Barybin MV, Ellis JE, Pomije MK, et al. Syntheses and Properties of Homoleptic Carbonyl and Trifluorophosphane Niobates: [Nb(CO)(6)](-), [Nb(PF(3))(6)](-) and [Nb(CO)(5)](3)(-) (,)(1). Inorg Chem. 1998;37(25):6518-6527doi: 10.1021/ic980752i.
Barybin, M. V., Ellis, J. E., Pomije, M. K., Tinkham, M. L., & Warnock, G. F. (1998). Syntheses and Properties of Homoleptic Carbonyl and Trifluorophosphane Niobates: [Nb(CO)(6)](-), [Nb(PF(3))(6)](-) and [Nb(CO)(5)](3)(-) (,)(1). Inorganic chemistry, 37(25), 6518-6527. https://doi.org/10.1021/ic980752i
Barybin, Mikhail V., et al. "Syntheses and Properties of Homoleptic Carbonyl and Trifluorophosphane Niobates: [Nb(CO)(6)](-), [Nb(PF(3))(6)](-) and [Nb(CO)(5)](3)(-) (,)(1)." Inorganic chemistry vol. 37,25 (1998): 6518-6527. doi: https://doi.org/10.1021/ic980752i
Barybin MV, Ellis JE, Pomije MK, Tinkham ML, Warnock GF. Syntheses and Properties of Homoleptic Carbonyl and Trifluorophosphane Niobates: [Nb(CO)(6)](-), [Nb(PF(3))(6)](-) and [Nb(CO)(5)](3)(-) (,)(1). Inorg Chem. 1998 Dec 14;37(25):6518-6527. doi: 10.1021/ic980752i. PMID: 11670773.
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Inorg Chem. 1998 Dec 14;37(25):6518-6527. doi: 10.1021/ic980752i.

Syntheses and Properties of Homoleptic Carbonyl and Trifluorophosphane Niobates: [Nb(CO)(6)](-), [Nb(PF(3))(6)](-) and [Nb(CO)(5)](3)(-) (,)(1).

Inorganic chemistry

Mikhail V. Barybin, John E. Ellis, Marie K. Pomije, Mary L. Tinkham, Garry F. Warnock

Affiliations

  1. Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455.

PMID: 11670773 DOI: 10.1021/ic980752i

Abstract

Reductive carbonylations of NbCl(4)(THF)(2), THF = tetrahydrofuran, mediated by sodium naphthalene in 1,2-dimethoxyethane, DME, or sodium anthracene in THF, provide [Nb(CO)(6)](-) as the tetraethylammonium salt in 60% or 70% isolated yields, respectively, the highest known for atmospheric pressure syntheses of this metal carbonyl. Corresponding reductions involving PF(3) give about 40% yields of [Et(4)N][Nb(PF(3))(6)], which in the past was only accessible by a photochemical route. Electrochemical data for [Nb(CO)(6)](-) and [Nb(PF(3))(6)](-) are compared and show that the PF(3) complex is almost 1 V more difficult to oxidize than the CO analogue. Protonation of [Nb(PF(3))(6)](-) by concentrated sulfuric acid yields a volatile, thermally unstable species, which has been shown by (1)H NMR and mass spectral studies to be the new niobium hydride, Nb(PF(3))(6)H. Previously unpublished (93)Nb and (13)C NMR studies corroborate prior claims that the sodium metal reduction of [Nb(CO)(6)](-) in liquid ammonia affords [Nb(CO)(5)](3)(-), the only known Nb(III-) species. The first details of this synthesis and those of [Nb(CO)(5)H](2)(-), [Nb(CO)(5)SnPh(3)](2)(-), [Nb(CO)(5)NH(3)](-), and [Nb(CO)(5)(CNtBu)](-) are presented.

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