Ring-Expanded N-Heterocyclic Carbene Complexes of Rhodium with Bifluoride, Fluoride, and Fluoroaryl Ligands

被引：23

作者：

Segarra, Candela ^{[1
]}

Mas-Marza, Elena ^{[1
]}

Lowe, John P. ^{[1
]}

Mahon, Mary F. ^{[2
]}

Poulten, Rebecca C. ^{[2
]}

Whittlesey, Michael K. ^{[1
]}

机构：

[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

[2] Univ Bath, Xray Crystallog Unit, Bath BA2 7AY, Avon, England

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 24期

基金：

英国工程与自然科学研究理事会;

关键词：

F BOND ACTIVATION; X-RAY; HYDRIDE BIFLUORIDE; NMR-SPECTROSCOPY; REACTIVITY; CHEMISTRY; CP-ASTERISK-2ZRH2; DEHYDROGENATION; REARRANGEMENT; COORDINATION;

D O I：

10.1021/om300984v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Thermolysis of Rh(PPh3)(4)H in the presence of the six-membered N-heterocyclic carbene 1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidine (6-Pr-i) gave the monocarbene complex Rh(6-Pr-i)(PPh3)(2)H as a 1:2 mixture of the cis- and trans-phosphine isomers la and 1b. This same isomeric mixture was formed as the ultimate product from treating Rh(PPh3)(3)(CO)H with 6-Pr-i at room temperature, although pathways involving both CO and PPh3 loss were observed at initial times. Treatment of 1a/1b with Et3N center dot 3HF generated the bifluoride complex cis-Rh(6-Pr-i)(PPh3)(2)(FHF) (2a), which upon stirring with anhydrous Me4NF was converted to the rhodium fluoride complex cis-Rh(6-Pr-i)(PPh3)(2)F (3a). Thermolysis of 1a/1b with C6F6 resulted in C-F bond activation to afford a mixture of 3a and the pentafluorophenyl complex trans-Rh(6-Pr-i)(PPh3)(2)(C6F5) (5b). Complexes 1b, 2a, 3a, and 5b were structurally characterized.

引用

页码：8584 / 8590

页数：7

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