Selective anion encapsulation by a metalated cryptophane with a π-acidic interior

被引：109

作者：

Fairchild, RM ^{[1
]}

Holman, KT ^{[1
]}

机构：

[1] Georgetown Univ, Dept Chem, Washington, DC 20057 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 47期

关键词：

D O I：

10.1021/ja055560i

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Metalation of the exterior arene faces of the molecular capsule (±)-cryptophane-E with [Cp*Ru]+ moieties results in a π-acidic cavity capable of encapsulating anions. The [CF3SO3]- and [SbF6]- salts have been crystallographically characterized and demonstrate the encapsulation of these anions by the metalated cryptophane. 1H and 19F NMR spectroscopy establish the binding of anions in NO2CD3 solution and reveal the relative affinity of the cavity for different anions (KX-/KOTf-): [BF4]- ≈ 0, [PF6]- = 1.18, [CF3SO3]- = 1, [SbF6]- = 0.30. Variable temperature rate studies reveal the activation barrier for triflate encapsulation to be ΔG‡298K = 18.0(8) kcal·mol-1 (ΔH‡ = 17.5(4) kcal·mol-1 and ΔS‡ = 2(1) cal·mol-1·K-1). Copyright © 2005 American Chemical Society.

引用

页码：16364 / 16365

页数：2

共 28 条

[1]

[Anonymous], COMPREHENSIVE SUPRAM

[2] Transition metal and organometallic anion complexation agents [J].

Beer, PD ;

Hayes, EJ .

COORDINATION CHEMISTRY REVIEWS, 2003, 240 (1-2) :167-189

[3]

Beer PD, 2001, ANGEW CHEM INT EDIT, V40, P486, DOI 10.1002/1521-3773(20010202)40:3<486::AID-ANIE486>3.3.CO

[4]

2-G

[5] Abiotic guanidinium containing receptors for anionic species [J].

Best, MD ;

Tobey, SL ;

Anslyn, EV .

COORDINATION CHEMISTRY REVIEWS, 2003, 240 (1-2) :3-15

[6] Amide based receptors for anions [J].

Bondy, CR ;

Loeb, SJ .

COORDINATION CHEMISTRY REVIEWS, 2003, 240 (1-2) :77-99

[7] STRUCTURE AND PROPERTIES OF THE CRYPTOPHANE-E CHCL3 COMPLEX, A STABLE VANDERWAALS MOLECULE [J].

CANCEILL, J ;

CESARIO, M ;

COLLET, A ;

GUILHEM, J ;

LACOMBE, L ;

LOZACH, B ;

PASCARD, C .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1989, 28 (09) :1246-1248

[8]

Cram D.J., 1994, CONTAINER MOL THEIR

[9] SYNTHESIS AND NUCLEOPHILIC-SUBSTITUTION OF HIGHLY CHLORINATED ARENE (ETA(5)-PENTAMETHYLCYCLOPENTADIENYL)RUTHENIUM PI-COMPLEXES [J].

DEMBEK, AA ;

FAGAN, PJ .

ORGANOMETALLICS, 1995, 14 (08) :3741-3745

[10] Anion-π interactions in a carousel copper(II)-triazine complex [J].

Demeshko, S ;

Dechert, S ;

Meyer, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (14) :4508-4509

← 1 2 3 →