Synthesis and chemistry of [hydrotris(3,5-bis(trifluoromethyl)pyrazolyl)borato]silver(I) complexes

被引:138
作者
Dias, HVR [1 ]
Wang, ZY [1 ]
Jin, WC [1 ]
机构
[1] Univ Texas, Dept Chem & Biochem, Arlington, TX 76019 USA
关键词
D O I
10.1021/ic9712028
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The syntheses, spectroscopy, and structures of silver(I) hydrotris(3,5-bis(trifluoromethyl)pyrazolyl)borate complexes with tetrahydrofuran (THF), toluene, carbon monoxide, ethylene, acetylene, phenylacetylene, tert-butyl isocyanide, and tert-butyl cyanide ligands are presented. These complexes can be synthesized conveniently starting from the sodium salt of [HB(3,5-(CF3)(2)Pz)(3)](-) ligand. The toluene ligand of [HB(3,5-(CF3)2Pz)(3)]Ag(eta(2)-toluene) exhibits fluxional behavior in solution and eta(2)-coordination in the solid state. The Ag-C distances, however, are not equal. The toluene ligand can be displaced reversibly with CO. [HB(3,5-(CF3)2Pz)(3)]AgCO has mainly a sigma-type Ag-CO bonding interaction. The Ag-C and C-O distances are 2.037(5) and 1.116(7) Angstrom, respectively. [HB-(3,5-(CF3)(2)Pz)(3)]Ag(H2C=CH2) and [HB(3,5-(CF3)(2)Pz)(3)]Ag(HC=CH) have similar solid state structures. The H2C=CH2 and HC=CH bind symmetrically to silver ion. The Ag-C distances of [HB(3,5-(CF3)(2)Pz)(3)]Ag(H2C=CH2) are 2.294(7) and 2.307(7) Angstrom. In [HB(3,5-(CF3)(2)Pz)(3)]Ag(HC=CPh), the alkyne unit coordinates to silver ion in an asymmetric fashion with Ag-C distances of 2.263(5) and 2.407(5) Angstrom. The upsilon(c=c) is about 69 cm(-1) lower than that for free HC=CPh. The coordinated alkyne moiety shows only a small bending-back angle (6.7 degrees). The C-C bond distances of H2C=CH2, HC=CH, and HC=CPh ligands remain virtually unchanged upon coordination to silver(I). [HB(3,5-(CF3)(2)Pz)(3)]AgCNBut has a relatively strong Ag-C bond. The isocyanide carbon resonance appears at delta 137.4 in the C-13 NMR spectrum. The upsilon(CN) band appears at 2214 cm(-1), which is about 76 cm(-1) higher than that for free CNBut. The Ag-C and C-N distances are 2.059(4) and 1.139(5) Angstrom, respectively. The isocyanide group is slightly bent with a Ag-C-N angle of 173.7(4)degrees and a C-N-C angle of 176.2(4)degrees. Structural features of [HB(3,5-(CF3)(2)Pz)(3)]AgNCBut are very similar to those of the CNBut analogue. The upsilon(NC) band appears at 2277 cm(-1). All these complexes show pseudo-tetrahedral silver centers with pyrazolyl N-Ag distances ranging from 2.297 to 2.447 Angstrom. The stability of these silver adducts may be primarily attributed to the unique electronic properties of the [HE (3,5-(CF3)(2)Pz)(3)](-) ligand.
引用
收藏
页码:6205 / 6215
页数:11
相关论文
共 119 条
[21]  
CHISHOLM MH, 1976, PROG INORG CHEM, V20, P299
[22]   DETERMINATION OF CRYSTAL-STRUCTURE AND MOLECULAR GEOMETRY OF [HYDROTRIS(1-PYRAZOLYL)BORATO]COPPER(I) CARBONYL - UNIQUE STRUCTURAL INVESTIGATION OF A COPPER-CARBONYL LINKAGE [J].
CHURCHILL, MR ;
DEBOER, BG ;
ROTELLA, FJ ;
ABUSALAH, OM ;
BRUCE, MI .
INORGANIC CHEMISTRY, 1975, 14 (09) :2051-2056
[23]  
COLLMAN JP, 1987, PRINCIPLES APPL ORGA, P57
[24]   X-RAY STRUCTURE OF NOVEL LIGAND-BRIDGED OLEFINIC TERTIARY ARSINE COMPLEX C11H15ASAG2(NO3)2 [J].
COOPER, MK ;
NYHOLM, RS ;
CARRECK, PW ;
MCPARTLIN, M .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1974, (09) :343-344
[25]  
Cotton FA, 1990, CHEM APPLICATIONS GR, P341
[26]   STUDIES ON METAL-ACETYLENE COMPLEXES .4. CRYSTAL-STRUCTURE OF BIS(TRIPHENYLPHOSPHINE)HEXAFLUOROBUT-2-YNEPLATINUM(0) [J].
DAVIES, BW ;
PAYNE, NC .
INORGANIC CHEMISTRY, 1974, 13 (08) :1848-1853
[27]  
DAVIES PB, 1984, J CHEM PHYS, V81, P1598, DOI 10.1063/1.447889
[28]   Novel tris(pyrazolyl)borates bearing perfluoroalkyl pigtails. Syntheses and characterization of the sodium and copper(I) complexes of [HB(3-(R)Pz)(3)](-) (R=C2F5, C3F7; Pz=pyrazolyl) [J].
Dias, HVR ;
Kim, HJ .
ORGANOMETALLICS, 1996, 15 (25) :5374-5379
[29]   Monomeric indium(I) and silver(I) complexes of a polyfluorinated tris(pyrazolyl)borate [J].
Dias, HVR ;
Jin, WC .
INORGANIC CHEMISTRY, 1996, 35 (01) :267-268
[30]   Coinage metal carbonyls and isocyanides: Synthesis and characterization of the gold(I)complexes [HB(3,5-(CF3)(2)Pz)(3)]AuCO and [HB(3,5-(CF3)(2)Pz)(3)]AuCNBu(t) [J].
Dias, HVR ;
Jin, WC .
INORGANIC CHEMISTRY, 1996, 35 (12) :3687-3694