Structural and reactivity comparison of analogous organometallic Pd(III) and Pd(IV) complexes

被引：49

作者：

Tang, Fengzhi ^{[1
]}

Qu, Fengrui ^{[1
]}

Khusnutdinova, Julia R. ^{[1
]}

Rath, Nigam P. ^{[2
]}

Mirica, Liviu M. ^{[1
]}

机构：

[1] Washington Univ, Dept Chem, St Louis, MO 63130 USA

[2] Univ Missouri, Dept Chem & Biochem, St Louis, MO 63121 USA

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 46期

关键词：

REDUCTIVE ELIMINATION-REACTIONS; PALLADIUM(IV) COMPLEXES; DIMETHYL COMPLEX; C-O; BOND; CHEMISTRY; CATALYSIS; OXIDATION; MACROCYCLES; FLUORIDE;

D O I：

10.1039/c2dt32127k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The tetradentate ligands (R)N4 (R(N)4 = N,N'-di-alkyl-2,11-diaza[3,3](2,6)pyridinophane, R = Me or iPr) were found to stabilize cationic ((R)N4)PdMe2 and ((R)N4)PdMeCl complexes in both Pd-III and Pd-IV oxidation states. This allows for the first time a direct structural and reactivity comparison of the two Pd oxidation states in an identical ligand environment. The Pd-III complexes exhibit a distorted octahedral geometry, as expected for a d(7) metal center, and display unselective C-C and C-Cl bond formation reactivity. By contrast, the PdIV complexes have a pseudo-octahedral geometry and undergo selective non-radical C-C or C-Cl bond formation that is controlled by the ability of the complex to access a five-coordinate intermediate.

引用

页码：14046 / 14050

页数：5

共 37 条

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