Palladium complexes bearing novel strongly bent trans-spanning diphosphine ligands: Synthesis, characterization, and catalytic activity

被引：64

作者：

Grossman, O ^{[1
]}

Azerraf, C ^{[1
]}

Gelman, D ^{[1
]}

机构：

[1] Hebrew Univ Jerusalem, Dept Organ Chem, IL-91904 Jerusalem, Israel

来源：

ORGANOMETALLICS | 2006年 / 25卷 / 02期

关键词：

D O I：

10.1021/om050906j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The new air-stable chelating diphosphine ligands 1,8-bis(diisopropylphosphino)triptycene (2) and 1-(diisopropylphosphino)-8-(diphenylphosphino)triptycene (3) were synthesized in 51-73% yield from readily available starting materials. The examination of their coordination modes in the palladium(H) complexes [PdCl2(2)] (4) and [PdCl2(3)] (5) by means of H-1, C-13 and P-31 NMR is consistent with the formation of trans-spanned complexes. X-ray analysis of 4 and 5 confirmed the structure but disclosed a strong distortion of the palladium centers from the expected square-planar geometry toward a butterfly-like environment. Further investigation revealed that 2 can also behave as a binucleating ligand, forming the quasi-closed halogen-bridged dipalladium complex 6, featuring an unusual nonplanar Pd-2(mu-Cl)(2)Cl-2 core. The catalytic activity of the new ligands and complexes was tested in palladium-catalyzed cross-coupling reactions of aryl chlorides with phenylboronic acid.

引用

页码：375 / 381

页数：7

共 90 条

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