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

Olga Grossman; Clarit Azerraf; Dmitri Gelman

doi:10.1021/om050906j

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

Olga Grossman, Clarit Azerraf, Dmitri Gelman^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

65 Scopus citations

Abstract

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(II) complexes [PdCl₂(2)] (4) and [PdCl₂(3)] (5) by means of ¹H, ¹³C, and ³¹P 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 Pd₂(μ-Cl) ₂Cl₂ core. The catalytic activity of the new ligands and complexes was tested in palladium-catalyzed cross-coupling reactions of aryl chlorides with phenylboronic acid.

Original language	English
Pages (from-to)	375-381
Number of pages	7
Journal	Organometallics
Volume	25
Issue number	2
DOIs	https://doi.org/10.1021/om050906j
State	Published - 16 Jan 2006

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

abstract = "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(II) complexes [PdCl2(2)] (4) and [PdCl2(3)] (5) by means of 1H, 13C, and 31P 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 Pd2(μ-Cl) 2Cl2 core. The catalytic activity of the new ligands and complexes was tested in palladium-catalyzed cross-coupling reactions of aryl chlorides with phenylboronic acid.",

author = "Olga Grossman and Clarit Azerraf and Dmitri Gelman",

year = "2006",

month = jan,

day = "16",

doi = "10.1021/om050906j",

language = "אנגלית",

volume = "25",

pages = "375--381",

journal = "Organometallics",

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T2 - Synthesis, characterization, and catalytic activity

AU - Grossman, Olga

AU - Azerraf, Clarit

AU - Gelman, Dmitri

PY - 2006/1/16

Y1 - 2006/1/16

N2 - 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(II) complexes [PdCl2(2)] (4) and [PdCl2(3)] (5) by means of 1H, 13C, and 31P 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 Pd2(μ-Cl) 2Cl2 core. The catalytic activity of the new ligands and complexes was tested in palladium-catalyzed cross-coupling reactions of aryl chlorides with phenylboronic acid.

AB - 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(II) complexes [PdCl2(2)] (4) and [PdCl2(3)] (5) by means of 1H, 13C, and 31P 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 Pd2(μ-Cl) 2Cl2 core. The catalytic activity of the new ligands and complexes was tested in palladium-catalyzed cross-coupling reactions of aryl chlorides with phenylboronic acid.

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

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