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)

Chi Ming Che; Kwok Yin Wong

doi:10.1039/DT9890002065

Notes. Oxo transfer reactions. Mechanistic studies on the oxidation of triphenylphosphine by trans-[ Ru^VIL(O)₂]²⁺ (L = 1,4,8,11 -tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane)

Research output: Journal article publication › Journal article › Academic research › peer-review

Abstract

The mechanism for the oxidation of PPh₃ to O=PPh₃ by trans- [ Ru^VIL(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 [Ru^VI]/dt = k₂[PPh₃] [Ru^VI]. 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-[Ru^VI(O)₂]²⁺ and [Ru^IV(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.

Original language	English
Pages (from-to)	2065-2067
Number of pages	3
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	10
DOIs	https://doi.org/10.1039/DT9890002065
Publication status	Published - 1 Jan 1989
Externally published	Yes

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@article{9387e8ee6d0c48119983e56ad2fce298,

title = "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)",

abstract = "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.",

author = "Che, {Chi Ming} and Wong, {Kwok Yin}",

year = "1989",

month = jan,

day = "1",

doi = "10.1039/DT9890002065",

language = "English",

pages = "2065--2067",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "10",

}

Notes. Oxo transfer reactions. Mechanistic studies on the oxidation of triphenylphosphine by trans-[ Ru^VIL(O)₂]²⁺ (L = 1,4,8,11 -tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane). / Che, Chi Ming; Wong, Kwok Yin.

In: Journal of the Chemical Society, Dalton Transactions, No. 10, 01.01.1989, p. 2065-2067.

Research output: Journal article publication › Journal article › Academic research › peer-review

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.

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U2 - 10.1039/DT9890002065

DO - 10.1039/DT9890002065

M3 - Journal article

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EP - 2067

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1472-7773

IS - 10

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Notes. Oxo transfer reactions. Mechanistic studies on the oxidation of triphenylphosphine by trans-[ Ru^VIL(O)₂]²⁺ (L = 1,4,8,11 -tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane)

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