Journal article
Mechanistic Studies of the Formation of Zirconium Alkylidene Complexes [η5-C5H3-1,3-(SiMe2CH2PPri2)2]ZrCHR(Cl) (R = Ph, SiMe3)
Journal of the American Chemical Society, Vol.121(11), pp.2478-2487
03/24/1999
DOI: 10.1021/ja982969h
Abstract
The reaction of [P2Cp]ZrC13 (1) with 2 equiv of KCH2Ph generates an equilibrium mixture of alkyl complexes consisting of [P2Cp]ZrCl2(CH2Ph) (2), [P2Cp]ZrCl(CH2Ph)2 (3), and [P2Cp]Zr(CH2Ph)3 (4). Thermolysis of this mixture yields the alkylidene complex [P2Cp]Zr=CHPh(Cl) (5) in 85% overall yield. Kinetic studies reveal a composite mechanism that incorporates the above preequilibrium, followed by an intramolecular α-abstraction reaction of dibenzyl 3 which follows a first-order rate, with the rate parameters ΔH((+)) = 19(1) kcal mol-1 and ΔS((+)) = -22(5) cal-1 mol K-1. A kinetic isotope effect of 3.0(5) was measured at 70°C for the perdeuterated analogue [P2Cp]ZrCl(CD2C6D5)2. The reaction of 1 with 2 equiv of LiCH2EMe3 (E = C, Si) produces a similar equilibrium mixture as observed for the benzyl analogues, consisting of [P2Cp]ZrCl2(CH2EMe3) (7), [P2Cp]Zr(CH2EMe3)3 (8), and [P2Cp]ZrCl(CH2EMe3)2 (9). Thermolysis of this mixture yields [P2Cp]Zr=CHEMe3(Cl) (6). A kinetic analysis conducted on 9 (E = Si) indicated a first-order reaction from which the activation parameters ΔH((+)) = 6(1) kcal mol-1 and ΔS((+)) = -62(5) cal mol-1 K-1 were obtained. The results indicate that reaction rates follow the order CH2Ph > CH2SiMe3 > CH2CMe3, an exact reversal of the trend for the homoleptic Ta systems Ta(CH2R)5. The role of phosphine coordination is discussed to account for this trend. A crystal structure determination obtained for 6b reveals an α-agostic interaction and a structure analogous to that of 5.
Details
- Title: Subtitle
- Mechanistic Studies of the Formation of Zirconium Alkylidene Complexes [η5-C5H3-1,3-(SiMe2CH2PPri2)2]ZrCHR(Cl) (R = Ph, SiMe3)
- Creators
- Michael D Fryzuk - Contribution from the Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, B.C., Canada V6T 1Z1, and Department of Chemistry, St. Mary's University,Halifax, N.S., Canada B3H 3C3Paul B Duval - Contribution from the Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, B.C., Canada V6T 1Z1, and Department of Chemistry, St. Mary's University,Halifax, N.S., Canada B3H 3C3Shane S. S. H Mao - Contribution from the Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, B.C., Canada V6T 1Z1, and Department of Chemistry, St. Mary's University,Halifax, N.S., Canada B3H 3C3Michael J Zaworotko - Contribution from the Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, B.C., Canada V6T 1Z1, and Department of Chemistry, St. Mary's University,Halifax, N.S., Canada B3H 3C3Leonard R Macgillivray - Contribution from the Department of Chemistry, University of British Columbia, 2036 Main Mall,Vancouver, B.C., Canada V6T 1Z1, and Department of Chemistry, St. Mary's University,Halifax, N.S., Canada B3H 3C3
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.121(11), pp.2478-2487
- Publisher
- American Chemical Society
- DOI
- 10.1021/ja982969h
- ISSN
- 0002-7863
- eISSN
- 1520-5126
- Language
- English
- Date published
- 03/24/1999
- Academic Unit
- Chemistry; Pharmaceutical Sciences and Experimental Therapeutics
- Record Identifier
- 9984216698302771
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