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

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. Finally, 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.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Max Planck Inst. für Chemische Energiekonversion, Stiftstraße (Germany)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1370932
Grant/Contract Number:  
SC0012702
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 24; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); materials and chemistry by design; synthesis (novel materials)

Citation Formats

Clouston, Laura J., Bernales, Varinia, Cammarota, Ryan C., Carlson, Rebecca K., Bill, Eckhard, Gagliardi, Laura, and Lu, Connie C. Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b01631.
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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. United States. https://doi.org/10.1021/acs.inorgchem.5b01631
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Clouston, Laura J., Bernales, Varinia, Cammarota, Ryan C., Carlson, Rebecca K., Bill, Eckhard, Gagliardi, Laura, and Lu, Connie C. Fri . "Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel". United States. https://doi.org/10.1021/acs.inorgchem.5b01631. https://www.osti.gov/servlets/purl/1370932.
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@article{osti_1370932,
title = {Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel},
author = {Clouston, Laura J. and Bernales, Varinia and Cammarota, Ryan C. and Carlson, Rebecca K. and Bill, Eckhard and Gagliardi, Laura and Lu, Connie C.},
abstractNote = {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. Finally, 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.},
doi = {10.1021/acs.inorgchem.5b01631},
journal = {Inorganic Chemistry},
number = 24,
volume = 54,
place = {United States},
year = {Fri Dec 04 00:00:00 EST 2015},
month = {Fri Dec 04 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acs.inorgchem.5b01631
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