Journal article
Reactivity Studies of the Zirconium Alkylidene Complexes [η5-C5H3-1,3-(SiMe2CH2PPri2)2]ZrCHR(Cl) (R = Ph, SiMe3)
Journal of the American Chemical Society, Vol.121(8), pp.1707-1716
03/03/1999
DOI: 10.1021/ja982695y
Abstract
Reactivity studies of the zirconium alkylidene complexes [P2Cp]Zr=CHR(Cl) (1a, R = Ph; 1b, R = SiMe3; [P2Cp] = η5-C5H3-1,3- (SiMe2CH2PPr(i)2)2) are described. The reaction of 1 with ethylene follows second-order kinetics to give the ethylene complex [P2Cp]Zr(η2- C2H4)Cl (2), the structure of which was determined by X-ray crystallography. Addition of acetone to 1 generates the alkene RCH=CMe2, although the anticipated Zr oxo species could not be isolated from this reaction. An insertion of CO into the Zr=C bond of 1 yields the ketene complex [P2Cp]Zr(η2-C,O-OC=CHR)Cl (3), while the reaction with tert-butyl isocyanide gives the analogous ketenimine complex [P2Cp]Zr(η2-C,N- Bu1NC=CHR)Cl (4). The Structure of ketene 3a (R = Ph), determined by X-ray diffraction, exhibits the E geometry, with the position of the ketene unit with respect to the ancillary [P2Cp] ligand being opposite to that in the configuration of the precursor alkylidene 1a. The ketene complex 3 reacts with ethylene to give [P2Cp]Zr(η2-C,O-CH2CH2C(O)=CHR)Cl (5). The molecular structure of 5b(R = SiMe3) was obtained by X-ray diffraction and reveals a five-membered zirconaoxacycle arising from the insertion of ethylene into the Zr-C bond of the ketene, which is subsequently coordinated to the metal as an enolate ligand. 5 undergoes a final insertion reaction with CO to give the asymmetric η2-acyl-ylide complex 6. For each reaction detailed above, dissociation of a labile pendant phosphine donor provides an open site for reactivity.
Details
- Title: Subtitle
- Reactivity Studies of the Zirconium Alkylidene Complexes [η5-C5H3-1,3-(SiMe2CH2PPri2)2]ZrCHR(Cl) (R = Ph, SiMe3)
- Creators
- Michael D Fryzuk - Contribution from the Departments of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, BC, Canada V6T 1Z1, and St. Mary's University, Halifax, NS, Canada B3H 3C3Paul B Duval - Contribution from the Departments of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, BC, Canada V6T 1Z1, and St. Mary's University, Halifax, NS, Canada B3H 3C3Shane S. S. H Mao - Contribution from the Departments of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, BC, Canada V6T 1Z1, and St. Mary's University, Halifax, NS, Canada B3H 3C3Steven J Rettig - Contribution from the Departments of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, BC, Canada V6T 1Z1, and St. Mary's University, Halifax, NS, Canada B3H 3C3Michael J Zaworotko - Contribution from the Departments of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, BC, Canada V6T 1Z1, and St. Mary's University, Halifax, NS, Canada B3H 3C3Leonard R Macgillivray - Contribution from the Departments of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, BC, Canada V6T 1Z1, and St. Mary's University, Halifax, NS, Canada B3H 3C3
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.121(8), pp.1707-1716
- Publisher
- American Chemical Society
- DOI
- 10.1021/ja982695y
- ISSN
- 0002-7863
- eISSN
- 1520-5126
- Language
- English
- Date published
- 03/03/1999
- Academic Unit
- Pharmaceutical Sciences and Experimental Therapeutics; Chemistry
- Record Identifier
- 9984216695502771
Metrics
3 Record Views