Comparative structural and thermodynamic studies of fluoride and cyanide binding by PhBMes2 and related triarylborane Lewis acids

被引:38
作者
Bresner, Christopher [1 ,2 ]
Haynes, Cally J. E. [1 ]
Addy, David A. [1 ]
Broomsgrove, Alexander E. J. [1 ]
Fitzpatrick, Philip [1 ]
Vidovic, Dragoslav [1 ]
Thompson, Amber L. [1 ]
Fallis, Ian A. [2 ]
Aldridge, Simon [1 ]
机构
[1] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England
[2] Cardiff Sch Chem, Cardiff CF10 3AT, S Glam, Wales
基金
英国工程与自然科学研究理事会;
关键词
BIFUNCTIONAL PERFLUOROARYL BORANES; SITE OLEFIN POLYMERIZATION; WEAKLY COORDINATING ANIONS; ELECTRON-ACCEPTING ABILITY; CHEMICAL WARFARE AGENTS; X-RAY-DIFFRACTION; BORONIC ACID; ION COMPLEXATION; CHARGE-TRANSFER; CATIONIC BORANE;
D O I
10.1039/c0nj00120a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Lewis acidic boranes containing the -BMes(2) unit (Mes = 2,4,6-Me3C6H2) have been widely exploited in molecular sensors for the fluoride ion reflecting, at least in part, the stability to air and moisture of derivatives of the type ArBMes(2). In the current study, the fluoride binding capabilities of the simplest such system, PhBMes(2) (1), have been investigated by spectroscopic and crystallographic methods, with a view to experimentally determining the fundamental thermodynamic and structural parameters associated with this host/guest interaction. A binding constant, K-F, of 8.9(1.9) x 10(4) M-1 in dichloromethane solution and a B-F bond length of 1.481(2) angstrom for the salt [(Bu4N)-Bu-n](+)[PhMes(2)BF](-) have thus been elucidated and provide a baseline for the analysis of more complex systems. Competitive binding of the cyanide ion is implied by a similar binding constant, K-CN, of 1.9(0.5) x 10(5) M-1; structurally, similar degrees of pyramidalization of the BC3 framework are observed on coordination of each anion {Sigma(C-B-C) = 339.8, 340.1 degrees for [(Bu4N)-Bu-n](+)[PhMes(2)BF](-) and [K(18-crown-6)](+)[PhMes(2)BCN](-), respectively}. Linking of two ArBMes(2) units via an alkyne spacer results in a 2,2'-bis(dimesitylboryl)tolan system, which is characterized by independent binding of two equivalents of the CN- anion, rather than cyanide chelation.
引用
收藏
页码:1652 / 1659
页数:8
相关论文
共 160 条
[11]   Enhanced fluorescence cyanide detection at physiologically lethal levels: Reduced ICT-based signal transduction [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (10) :3635-3641
[12]   Cyanide-sensitive fluorescent probes [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
DYES AND PIGMENTS, 2005, 64 (01) :49-55
[13]   Wavelength-ratiometric probes for the selective detection of fluoride based on the 6-aminoquinolinium nucleus and boronic acid moiety [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
JOURNAL OF FLUORESCENCE, 2004, 14 (06) :693-703
[14]   Fluorescence intensity and lifetime-based cyanide sensitive probes for physiological safeguard [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
ANALYTICA CHIMICA ACTA, 2004, 522 (01) :9-17
[15]   Excitation and emission wavelength ratiometric cyanide-sensitive probes for physiological sensing [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
ANALYTICAL BIOCHEMISTRY, 2004, 327 (01) :82-90
[16]   A wavelength-ratiometric fluoride-sensitive probe based on the quinolinium nucleus and boronic acid moiety [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
SENSORS AND ACTUATORS B-CHEMICAL, 2005, 104 (01) :103-110
[17]   Anion sensing using quinolinium based boronic acid probes [J].
Badugu, R ;
Lakowicz, JR ;
Geddes, CD .
CURRENT ANALYTICAL CHEMISTRY, 2005, 1 (02) :157-170
[18]  
Baskin S.I., 1997, TXB MILITARY MED MED, P271
[19]   Cyanide: critical issues in diagnosis and treatment [J].
Baud, F. J. .
HUMAN & EXPERIMENTAL TOXICOLOGY, 2007, 26 (03) :191-201
[20]   Transition metal and organometallic anion complexation agents [J].
Beer, PD ;
Hayes, EJ .
COORDINATION CHEMISTRY REVIEWS, 2003, 240 (1-2) :167-189