Journal article
Reduction of Carbon Monoxide by Tandem Electron Transfer and Migratory Insertion of a Masked Zirconium(IV) Hydride. Formation of a Zirconium Formyl−Ylide Complex
Organometallics, Vol.15(4), pp.1134-1138
02/20/1996
DOI: 10.1021/om950302n
Abstract
In the presence of carbon monoxide, the Zr(III) tetrahydroborate complex Zr(η5-C5H5)BH4[N(SiMe 2CH2PPr2i)2] disproportionates to give two diamagnetic species: the bis-(tetrahydroborate) complex Zr(η5-C5H5)(BH4) 2[N(SiMe2CH2PPr2i) 2] and the dicarbonyl derivative Zr(η5-C5H5)(CO)2[N(SiMe 2CH2PPr2i)2]. The bis(tetrahydroborate) undergoes a further slow reaction with CO to generate a zirconium-formyl complex in which the formyl unit is stabilized by phosphine coordination; in other words, electron transfer in tandem with hydride migratory insertion have been used to reduce CO. The structure of the formyl-ylide species Zr(η5-C5H5)(BH4)(HCOPPr 2iCH2SiMe2)N(SiMe2CH 2PPr2iBH3) was determined by both solution (NMR spectroscopy) and solid-state (X-ray crystallography) methods. Not only does one end of the tridentate amido-diphosphine ligand bind to the formyl carbon but the other phosphine donor is coordinated to a BH3 molecule. Presumably, it is this latter interaction that initially frees up a reactive Zr-H bond that subsequently undergoes migratory insertion with CO to generate the formyl unit.
Details
- Title: Subtitle
- Reduction of Carbon Monoxide by Tandem Electron Transfer and Migratory Insertion of a Masked Zirconium(IV) Hydride. Formation of a Zirconium Formyl−Ylide Complex
- Creators
- Michael D Fryzuk - Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, British Columbia V6T 1Z1, CanadaMurugesapillai Mylvaganam - Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, British Columbia V6T 1Z1, CanadaMichael J Zaworotko - Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, British Columbia V6T 1Z1, CanadaL. R Macgillivray - Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, British Columbia V6T 1Z1, Canada
- Resource Type
- Journal article
- Publication Details
- Organometallics, Vol.15(4), pp.1134-1138
- Publisher
- American Chemical Society
- DOI
- 10.1021/om950302n
- ISSN
- 0276-7333
- eISSN
- 1520-6041
- Language
- English
- Date published
- 02/20/1996
- Academic Unit
- Chemistry; Pharmaceutical Sciences and Experimental Therapeutics
- Record Identifier
- 9984216614502771
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