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“Oxidative Addition” to a Zirconium(IV) Redox-Active Ligand Complex
Abstract
A strategy to enable reactivity analogous to oxidative addition is presented for d(0) transition-metal complexes. The reaction of the redox-active ligand 2,4-di-tert-butyl-6-tert-butylamidophenolate (ap) with ZrCl(4)(THF)(2) affords the new complex Zr(IV)(ap)(2)(THF)(2). This compound is formally zirconium(IV) and contains no d electrons; however, exposure of Zr(IV)(ap)(2)(THF)(2) to chlorine gas results in swift chlorine addition at the zirconium metal center via one-electron oxidation of each ap ligand. The diradical product, Zr(IV)Cl(2)(isq)(2) (isq = 2,4-di-tert-butyl-6-tert-butyliminosemiquinone), has been characterized by X-ray crystallography, electron paramagnetic resonance spectroscopy, and SQUID magnetometery.
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Citations
Cited by
Manifestations of Noninnocent Ligand Behavior
Kaim, W. (2011) · Inorganic Chemistry · doi:10.1021/ic2003832 · Cited by 498
The Shrinking World of Innocent Ligands: Conventionaland Non‐Conventional Redox‐Active Ligands
Kaim, W. (2012) · European Journal of Inorganic Chemistry · doi:10.1002/ejic.201101359 · Cited by 290
Dopamine complexes of iron in the etiology and pathogenesis of Parkinson’s disease
ARREGUIN, S., NELSON, P., PADWAY, S., SHIRAZI, M., & PIERPONT, C. (2009) · Journal of Inorganic Biochemistry · doi:10.1016/j.jinorgbio.2008.09.007 · Cited by 55
Metadata
- Authors
- Blackmore, K. J., Ziller, J. W., & Heyduk, A. F.
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2005-07-09
- Volume
- 44
- Issue
- 16
- Pages
- 5559-5561
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- OpenAlex
- W2015697377
- Cited by
- 169
- References
- 0
- FWCI
- 3.57
- Type
- journal article
- Language
- en
- Open access
- closed
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- CoChat. (2026). Citation check: “Oxidative Addition” to a Zirconium(IV) Redox-Active Ligand Complex. https://app.cochat.ai/papers/10.1021/ic050997c
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- Blackmore, K. J., Ziller, J. W., & Heyduk, A. F. (2005). “Oxidative Addition” to a Zirconium(IV) Redox-Active Ligand Complex. Inorganic Chemistry. https://doi.org/10.1021/ic050997c
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