Oxygen Binding to [Pd(L)(L′)] (L= NHC, L′ = NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex

被引：51

作者：

Cai, Xiaochen ^{[1
]}

Majumdar, Subhojit ^{[1
]}

Fortman, George C. ^{[1
,2
]}

Cazin, Catherine S. J. ^{[2
]}

Slawin, Alexandra M. Z. ^{[2
]}

Lhermitte, Charles ^{[1
]}

Prabhakar, Rajeev ^{[1
]}

Germain, Meaghan E. ^{[3
]}

Palluccio, Taryn ^{[3
]}

Nolan, Steven P. ^{[2
]}

Rybak-Akimova, Elena V. ^{[3
]}

Temprado, Manuel ^{[4
]}

Captain, Burjor ^{[1
]}

Hoff, Carl D. ^{[1
]}

机构：

[1] Univ Miami, Dept Chem, Coral Gables, FL 33146 USA

[2] Univ St Andrews, EaStCHEM Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[3] Tufts Univ, Dept Chem, Medford, MA 02155 USA

[4] Univ Alcala de Henares, Dept Phys Chem, Madrid 28801, Spain

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 05期

基金：

美国国家科学基金会; 英国工程与自然科学研究理事会;

关键词：

MOLECULAR-OXYGEN; ORGANIC-CHEMICALS; AEROBIC OXIDATION; DIOXYGEN; PHOSPHINE; HYDRIDE; PEROXO; HYDROPEROXIDE; CATALYSIS; INSERTION;

D O I：

10.1021/ja1103348

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity of a number of two-coordinate [Pd(L)(L')] (L = N-heterocyclic carbene (NHC) and L' = NHC or PR3) complexes with O-2 has been examined. Stopped-flow kinetic studies show that O-2 binding to [Pd(IPr)(P(p-tolyl)(3))] to form cis-[Pd(IPr)(P(p-tolyl)(3))-(eta(2)-O-2)] occurs in a rapid, second-order process. The enthalpy of O-2 binding to the Pd(0) center has been determined by solution calorimetry to be -26.2(1.9) kcal/mol. Extension of this work to the bis-NHC complex [Pd(IPr)(2)], however, did not lead to the formation of the expected diamagnetic complex cis-[Pd(IPr)(2)(eta(2)-O-2)] but to paramagnetic trans-[(Pd(IPr)(2)(eta(1)-O-2)(2)], which has been fully characterized. Computational studies addressing the energetics of O-2 binding have been performed and provide insight into reactivity changes as steric pressure is increased.

引用

页码：1290 / 1293

页数：4

共 33 条

[1] Mechanism of the palladium-catalyzed homocoupling of arylboronic acids: Key involvement of a palladium peroxo complex
Adamo, Carlo
Amatore, Christian
Ciofini, Ilaria
Jutand, Anny
Lakmini, Hakim
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (21) : 6829 - 6836
[2] Palladium(II)-Catalyzed C-H Activation/C-C Cross-Coupling Reactions: Versatility and Practicality
Chen, Xiao
Engle, Keary M.
Wang, Dong-Hui
Yu, Jin-Quan
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (28) : 5094 - 5115
[3] Percent buried volume for phosphine and N-heterocyclic carbene ligands: steric properties in organometallic chemistry
Clavier, Herve
Nolan, Steven P.
[J]. CHEMICAL COMMUNICATIONS, 2010, 46 (06) : 841 - 861
[4] Carbenes: Synthesis, properties, and organometallic chemistry
de Fremont, Pierre
Marion, Nicolas
Nolan, Steven P.
[J]. COORDINATION CHEMISTRY REVIEWS, 2009, 253 (7-8) : 862 - 892
[5] Insertion of molecular oxygen into a palladium(II) hydride bond
Denney, MC
Smythe, NA
Cetto, KL
Kemp, RA
Goldberg, KI
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (08) : 2508 - 2509
[6] N-Heterocyclic Carbenes in Late Transition Metal Catalysis
Diez-Gonzalez, Silvia
Marion, Nicolas
Nolan, Steven P.
[J]. CHEMICAL REVIEWS, 2009, 109 (08) : 3612 - 3676
[7] A general synthetic route to mixed NHC-phosphane palladium(0) complexes (NHC = N-heterocyclic carbene)
Fantasia, Serena
Nolan, Steven P.
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (23) : 6987 - 6993
[8] Solution Calorimetric Study of Ligand Exchange Reactions in the [Au(L)Cl] System (L = Phosphine and Phosphite)
Fortman, George C.
Nolan, Steven P.
[J]. ORGANOMETALLICS, 2010, 29 (20) : 4579 - 4583
[9] Unusual reactivities of N-heterocyclic carbenes upon coordination to the platinum(II)-dimethyl moiety
Fortman, George C.
Scott, Natalie M.
Linden, Anthony
Stevens, Edwin D.
Dorta, Reto
Nolan, Steven P.
[J]. CHEMICAL COMMUNICATIONS, 2010, 46 (07) : 1050 - 1052
[10] Recent advancements and challenges of palladiumII-catalyzed oxidation reactions with molecular oxygen as the sole oxidant
Gligorich, Keith M.
Sigman, Matthew S.
[J]. CHEMICAL COMMUNICATIONS, 2009, (26) : 3854 - 3867

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