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  Isolation of a Homoleptic Non-Oxo Mo(V) Alkoxide Complex: Synthesis, Structure and Electronic Properties of Penta-tert-Butoxymolybdenum

Hillenbrand, J., van Gastel, M., Bill, E., Neese, F., & Fürstner, A. (2020). Isolation of a Homoleptic Non-Oxo Mo(V) Alkoxide Complex: Synthesis, Structure and Electronic Properties of Penta-tert-Butoxymolybdenum. Journal of the American Chemical Society, 142(38), 16392-16402. doi:10.1021/jacs.0c07073.

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 Creators:
Hillenbrand, Julius1, Author           
van Gastel, Maurice2, Author           
Bill, Eckhard3, Author           
Neese, Frank4, Author           
Fürstner, Alois1, Author           
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
3Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
4Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Abstract: Treatment of [MoCl4(THF)2] with MOtBu (M = Na, Li) does not result in simple metathetic ligand exchange but entails disproportionation with formation of the well-known dinuclear complex [(tBuO)3Mo≡Mo(OtBu)3] and a new paramagnetic compound, [Mo(OtBu)5]. This particular five-coordinate species is the first monomeric, homoleptic, all-oxygen-ligated but non-oxo 4d1 Mo(V) complex known to date; as such, it proves that the dominance of the Mo=O group over (high-valent) molybdenum chemistry can be challenged. [Mo(OtBu)5] was characterized in detail by a combined experimental/computational approach using X-ray diffraction; UV/vis, MCD, IR, EPR, and NMR spectroscopy; and quantum chemistry. The recorded data confirm a Jahn–Teller distortion of the structure, as befitting a d1 species, and show that the complex undergoes Berry pseudorotation. The alkoxide ligands render the disproportionation reaction, leading the formation of [Mo(OtBu)5] to be particularly facile, even though the parent complex [MoCl4(THF)2] itself was also found to be intrinsically unstable; remarkably, this substrate converts into a crystalline material, in which the newly formed Mo(III) and Mo(V) products cohabitate the same unit cell.

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Language(s): eng - English
 Dates: 2020-07-012020-08-262020-09-23
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.0c07073
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (38) Sequence Number: - Start / End Page: 16392 - 16402 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870