TY - JOUR
T1 - Mechanistic studies of the formation of zirconium alkylidene complexes [η5-C5H3-1,3-(SiMe2CH2PPr(i)2)2]Zr=CHR(Cl) (R = Ph, SiMe3)
AU - Fryzuk, M. D.
AU - Duval, P. B.
AU - Mao, S. S.S.H.
AU - Zaworotko, M. J.
AU - MacGillivray, L. R.
PY - 1999/3/24
Y1 - 1999/3/24
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0033599482&partnerID=8YFLogxK
U2 - 10.1021/ja982969h
DO - 10.1021/ja982969h
M3 - Article
AN - SCOPUS:0033599482
SN - 0002-7863
VL - 121
SP - 2478
EP - 2487
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 11
ER -