TY - JOUR
T1 - Notes. Oxo transfer reactions. Mechanistic studies on the oxidation of triphenylphosphine by trans-[ RuVIL(O)2]2+ (L = 1,4,8,11 -tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane)
AU - Che, Chi Ming
AU - Wong, Kwok Yin
PY - 1989/1/1
Y1 - 1989/1/1
N2 - The mechanism for the oxidation of PPh3 to O=PPh3 by trans- [ RuVIL(O)2]2+ (L = 1,4,8,11- tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane) in CH3CN was studied from 280 to 299 K. The rate law for the reaction is d [RuVI]/dt = k2[PPh3] [RuVI]. At 299 K, k2, is (1.28 ± 0.1) × 102 dm3 mol-1 s-1. The ΔH‡ and ΔS‡ values are (8.7 ± 0.8) kcal mol-1 and -20 ± 2 cal K-1 mol-1 respectively. A direct comparison between the reactivities of trans-[RuVI(O)2]2+ and [RuIV(bipy)2(py)(O)]2+ (bipy = 2,2′- bipyridine; py = pyridine) towards the oxidation of PPh3 shows the ruthenium(IV) complex to react 1 000 times faster.
AB - The mechanism for the oxidation of PPh3 to O=PPh3 by trans- [ RuVIL(O)2]2+ (L = 1,4,8,11- tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane) in CH3CN was studied from 280 to 299 K. The rate law for the reaction is d [RuVI]/dt = k2[PPh3] [RuVI]. At 299 K, k2, is (1.28 ± 0.1) × 102 dm3 mol-1 s-1. The ΔH‡ and ΔS‡ values are (8.7 ± 0.8) kcal mol-1 and -20 ± 2 cal K-1 mol-1 respectively. A direct comparison between the reactivities of trans-[RuVI(O)2]2+ and [RuIV(bipy)2(py)(O)]2+ (bipy = 2,2′- bipyridine; py = pyridine) towards the oxidation of PPh3 shows the ruthenium(IV) complex to react 1 000 times faster.
UR - http://www.scopus.com/inward/record.url?scp=37049072028&partnerID=8YFLogxK
U2 - 10.1039/DT9890002065
DO - 10.1039/DT9890002065
M3 - Journal article
SP - 2065
EP - 2067
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
SN - 1472-7773
IS - 10
ER -