Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel

Laura J. Clouston, Varinia Bernales, Ryan C. Cammarota, Rebecca K. Carlson, Eckhard Bill, Laura Gagliardi, Connie C. Lu

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Zero-valent iron, cobalt, and nickel were installed into the metalloligand V[N(o-(NCH2P(iPr)2)C6H4)3] (1, VL), generating the heterobimetallic trio FeVL (2), CoVL (3), and NiVL (4), respectively. In addition, the one-electron-oxidized analogues [FeVL]X ([2ox]X, where X- = BPh4 or PF6) and [CoVL]BPh4 ([3ox]BPh4) were prepared. The complexes were characterized by a host of physical methods, including cyclic voltammetry, X-ray crystallography, magnetic susceptibility, electronic absorption, NMR, electron paramagnetic resonance (EPR), and Mössbauer spectroscopies. The CoV and FeV heterobimetallic compounds have short M-V bond lengths that are consistent with M-M multiple bonding. As revealed by theoretical calculations, the M-V bond is triple in 2, 2ox, and 3ox, double in 3, and dative (Ni → V) in 4. The (d-d)10 species, 2 and 3ox, are diamagnetic and exhibit large diamagnetic anisotropies of '4700 × 10-36 m3/molecule. Complexes 2 and 3ox are also characterized by intense visible bands at 760 and 610 nm (ε > 1000 M-1 cm-1), respectively, which correspond to an intermetal (M → V) charge-transfer transition. Magnetic susceptibility measurements and EPR characterization establish S = 1/2 ground states for (d-d)9 2ox and (d-d)11 3, while (d-d)12 4 is S = 1 based on Evans' method.

Original languageEnglish (US)
Pages (from-to)11669-11679
Number of pages11
JournalInorganic Chemistry
Volume54
Issue number24
DOIs
StatePublished - Dec 21 2015

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Vanadium
Cobalt
Nickel
Magnetic susceptibility
vanadium
Paramagnetic resonance
electron paramagnetic resonance
cobalt
Iron
nickel
magnetic permeability
iron
X ray crystallography
Bond length
Ground state
Cyclic voltammetry
crystallography
Charge transfer
Anisotropy
charge transfer

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Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel. / Clouston, Laura J.; Bernales, Varinia; Cammarota, Ryan C.; Carlson, Rebecca K.; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

In: Inorganic Chemistry, Vol. 54, No. 24, 21.12.2015, p. 11669-11679.

Research output: Contribution to journalArticle

Clouston, LJ, Bernales, V, Cammarota, RC, Carlson, RK, Bill, E, Gagliardi, L & Lu, CC 2015, 'Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel', Inorganic Chemistry, vol. 54, no. 24, pp. 11669-11679. https://doi.org/10.1021/acs.inorgchem.5b01631
Clouston LJ, Bernales V, Cammarota RC, Carlson RK, Bill E, Gagliardi L et al. Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel. Inorganic Chemistry. 2015 Dec 21;54(24):11669-11679. https://doi.org/10.1021/acs.inorgchem.5b01631
Clouston, Laura J. ; Bernales, Varinia ; Cammarota, Ryan C. ; Carlson, Rebecca K. ; Bill, Eckhard ; Gagliardi, Laura ; Lu, Connie C. / Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 24. pp. 11669-11679.
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AB - Zero-valent iron, cobalt, and nickel were installed into the metalloligand V[N(o-(NCH2P(iPr)2)C6H4)3] (1, VL), generating the heterobimetallic trio FeVL (2), CoVL (3), and NiVL (4), respectively. In addition, the one-electron-oxidized analogues [FeVL]X ([2ox]X, where X- = BPh4 or PF6) and [CoVL]BPh4 ([3ox]BPh4) were prepared. The complexes were characterized by a host of physical methods, including cyclic voltammetry, X-ray crystallography, magnetic susceptibility, electronic absorption, NMR, electron paramagnetic resonance (EPR), and Mössbauer spectroscopies. The CoV and FeV heterobimetallic compounds have short M-V bond lengths that are consistent with M-M multiple bonding. As revealed by theoretical calculations, the M-V bond is triple in 2, 2ox, and 3ox, double in 3, and dative (Ni → V) in 4. The (d-d)10 species, 2 and 3ox, are diamagnetic and exhibit large diamagnetic anisotropies of '4700 × 10-36 m3/molecule. Complexes 2 and 3ox are also characterized by intense visible bands at 760 and 610 nm (ε > 1000 M-1 cm-1), respectively, which correspond to an intermetal (M → V) charge-transfer transition. Magnetic susceptibility measurements and EPR characterization establish S = 1/2 ground states for (d-d)9 2ox and (d-d)11 3, while (d-d)12 4 is S = 1 based on Evans' method.

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