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

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [1];  [2];  [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Max Planck Inst. für Chemische Energiekonversion, Stiftstraße (Germany)
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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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012702
OSTI ID:
1370932
Journal Information:
Inorganic Chemistry, Vol. 54, 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; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 36 works
Citation information provided by
Web of Science

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  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
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Cited By (11)

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Heterobimetallic and Heterotrimetallic Clusters Containing a Redox-Active Metalloligand: Heterobimetallic and Heterotrimetallic Clusters Containing a Redox-Active Metalloligand journal December 2017
Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes journal January 2017
Playing with Pearson's concept: orthogonally functionalized 1,4-diaza-1,3-butadienes leading to heterobinuclear complexes journal January 2018
Heterobimetallic scandium–group 10 metal complexes with LM → Sc (LM = Ni, Pd, Pt) dative bonds journal January 2020
The bond length and bond energy of gaseous CrW journal June 2016
Synthesis, structure and magnetic property of a copper(II)–cobalt(II) heteronuclear complex with Schiff base ligand journal December 2019
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (heterogeneous)
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