TY - JOUR

T1 - Polystyrene-Supported Acyclic Diaminocarbene Palladium Complexes in Sonogashira Cross-Coupling: Stability vs. Catalytic Activity

AU - Михайлов, Владимир Николаевич

AU - Сорокоумов, Виктор Николаевич

AU - Ляхов, Денис Мартин Игоревич

AU - Цховребов, Александр Георгиевич

AU - Балова, Ирина Анатольевна

N1 - Funding Information: Acknowledgments: This study was supported by Saint Petersburg State University (project 12.40.515.2017). V.N.M. is grateful to the Russian Foundation for Basic Research (research project for young scientists No. 16-33-00659 mol_a). The research was carried out by using the equipment of Resource Centers of Saint Petersburg State University Science park: Centre of Magnetic Resonance, Chemistry Educational Centre, Centre for Chemical Analysis and Materials Research, Centre for X-ray Diffraction Studies (special thanks to Suslonov Vitaly for the help with structure elucidation), Center of Physical methods of surface investigation.

PY - 2018/4/2

Y1 - 2018/4/2

N2 - Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-Pd II ) are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-Pd II , systems are found to have different catalytic activity and stability regarding Pd-leaching. Pd II -diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd 0 -containing species providing a catalytic “cocktail system” with high activity and ability to reuse within nine runs. Polymer-supported palladium (II) complex bearing NBn–C carbene –NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-Pd II complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-Pd II conversion through carbodiimide into an active Pd 0 forms.

AB - Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-Pd II ) are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-Pd II , systems are found to have different catalytic activity and stability regarding Pd-leaching. Pd II -diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd 0 -containing species providing a catalytic “cocktail system” with high activity and ability to reuse within nine runs. Polymer-supported palladium (II) complex bearing NBn–C carbene –NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-Pd II complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-Pd II conversion through carbodiimide into an active Pd 0 forms.

KW - activation

KW - boomerang mechanism

KW - carbene

KW - sonogashira coupling

KW - polystyrene

KW - palladium

KW - isocyanide

KW - Boomerang mechanism

KW - Carbene

KW - Carbodiimide

KW - Catalyst activation

KW - Cross-coupling

KW - Isocyanide

KW - Palladium

KW - Polystyrene

KW - Sonogashira coupling

UR - http://www.scopus.com/inward/record.url?scp=85045077242&partnerID=8YFLogxK

U2 - 10.3390/catal8040141

DO - 10.3390/catal8040141

M3 - Article

VL - 8

SP - 141

JO - Catalysts

JF - Catalysts

SN - 2073-4344

IS - 4

M1 - 141

ER -