Relationship between the anion/cation relative orientation and the catalytic activity of nitrogen acyclic carbene-gold catalysts

被引：28

作者：

Biasiolo, L. ^{[1
,2
]}

Ciancaleoni, G. ^{[2
]}

Belpassi, L. ^{[2
]}

Bistoni, G. ^{[2
,3
]}

Macchioni, A. ^{[3
]}

Tarantelli, F. ^{[3
]}

Zuccaccia, D. ^{[1
]}

机构：

[1] Univ Udine, Dipartimento Chim Fis & Ambiente, I-33100 Udine, Italy

[2] Univ Perugia, Ist Sci & Tecnol Mol CNR CNR ISTM, Dipartimento Chim, I-06123 Perugia, Italy

[3] Univ Perugia, Dipartimento Dipartimento Chim Biol & Biotecnol, I-06123 Perugia, Italy

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2015年 / 5卷 / 03期

关键词：

ALPHA-DIIMINE LIGANDS; PGSE-NMR MEASUREMENTS; ION-PAIR STRUCTURE; GOLD(I)-CATALYZED HYDROALKOXYLATION; HETEROCYCLIC CARBENES; MECHANISTIC INSIGHTS; RUTHENIUM(II) SALTS; PROTON-TRANSFER; COMPLEXES; COUNTERION;

D O I：

10.1039/c4cy01440e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We elucidate the role of the ligand in determining the ion pair structure of the [(NAC)Au(eta(2)-3-hexyne)](+) BF4-(NAC = Nitrogen Acyclic Carbene, also known as ADC = Acyclic Diamino Carbene) catalysts and how the position of the anion influences their catalytic performance, giving a detailed relationship between the ion pair structure, determined by F-19, H-1-HOESY NMR experiments and DFT calculations, and the catalytic activity in the intermolecular alkoxylation of alkynes. From our results, it is evident that if the anion is forced to be far from the catalytic site by ancillary ligand-anion hydrogen bonding interactions, the reaction slows down. On the contrary, if the anion is located near the alkynes the reaction is accelerated, coherent with the proposed active role of the anion in catalysis. These results open new opportunities in ligand design for the gold-mediated reactions in which the anion plays an important role during the catalysis.

引用

页码：1558 / 1567

页数：10

共 69 条

[31] Biarylphosphonite Gold(I) Complexes as Superior Catalysts for Oxidative Cyclization of Propynyl Arenes into Indan-2-ones [J].