The Effect of a Fourth Binding Site on the Stabilization of Cationic SPS Pincer Palladium Complexes: Experimental, DFT, and Mass Spectrometric Studies

被引:9
作者
Blug, Matthias [1 ]
Doux, Marjolaine [1 ]
Le Goff, Xavier [1 ]
Maitre, Philippe [2 ]
Ribot, Francois [3 ]
Le Floch, Pascal [1 ]
Mezailles, Nicolas [1 ]
机构
[1] Ecole Polytech, Lab Heteroelements & Coordinat, CNRS, F-91128 Palaiseau, France
[2] Univ Paris 11, Chim Phys Lab, CNRS, F-91405 Orsay, France
[3] Univ Paris 06, UPMC, F-75252 Paris, France
关键词
CATALYZED ELECTROPHILIC SUBSTITUTION; ORGANOMETALLIC CHEMISTRY; CONTINUUM MODEL; AB-INITIO; DIFFUSION; REGIOSELECTIVITY; SPECTROSCOPY; ALLYLATION; REACTIVITY; MOLECULES;
D O I
10.1021/om800690t
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A potentially tetradentate ligand was synthesized by the addition of alpha-Li-picoline to the 2,6-bis(diphenylphosphine sulfide)-3,5-diphenylphosphinine (SPS) ligand. The corresponding Pd complex (3) was obtained by the reaction with [(COD)PdCl2]. An air-stable cationic Pd(II) complex (4) was obtained after abstraction of Cl- with silver salt. The role of the additional binding site in the stabilization of the cationic complex was explored using NMR spectroscopic and tandem ESI-MS studies combined with DFT calculations. Additionally the picoline moiety was used to tune the electronic properties of the cationic complex 7 to modify the activity in the Lewis acid-catalyzed allylation of aldehydes.
引用
收藏
页码:2020 / 2027
页数:8
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