Sirianni Eric R, Yap Glenn P A, Akturk Eser S, Theopold Klaus H
Department of Chemistry and Biochemistry, Center for Catalytic Science and Technology, University of Delaware, Brown Laboratory, Newark, DE 19716, USA.
Acta Crystallogr C. 2013 Sep;69(Pt 9):947-53. doi: 10.1107/S0108270113015898. Epub 2013 Aug 3.
Improvements in the syntheses of the carboxamide-substituted tris(pyrazolyl)borate ligands Tp(CONHPh,Me) [tris(3-anilinocarbonyl-5-methylpyrazol-1-yl)borate] and Tp(CONHt-Bu,Me) [tris(3-tert-butylaminocarbonyl-5-methylpyrazol-1-yl)borate] are reported. Their Tl(I) salts, namely [tris(3-anilinocarbonyl-5-methylpyrazol-1-yl-κN(2))borato]thallium(I), [Tl(C33H31BN9O3)], (II), and [tris(3-tert-butylaminocarbonyl-5-methylpyrazol-1-yl-κN(2))borato]thallium(I), [Tl(C27H43BN9O3)], (III), as well as the Cu(I) carbonyl complexes (Tp(CONHPh,Me))Cu(CO), namely carbonyl[tris(3-anilinocarbonyl-5-methylpyrazol-1-yl-κN(2))borato]copper(I) tetrahydrofuran trisolvate, [Cu(C33H31BN9O3)(CO)]·3C4H8O, (IV), and (Tp(CONHt-Bu,Me))Cu(CO), namely carbonyl[tris(3-tert-butylaminocarbonyl-5-methylpyrazol-1-yl-κN(2))borato]copper(I) tetrahydrofuran hemisolvate, [Cu(C27H43BN9O3)(CO)]·0.5C4H8O, (V), have been prepared. Their spectroscopic properties and structures are compared with those of related compounds. The molecules of (II)-(V) show hydrogen bonding to either solvent molecules or neighboring complex molecules via amide groups. The title compounds feature the ability to engage other ligands in hydrogen bonding and they show strong electron-withdrawing character. Compound (V) displays voids of ca 800 Å(3) in the crystal structure.
报道了羧酰胺取代的三（吡唑基）硼酸酯配体Tp（CONHPh，Me）[三（3-苯胺羰基-5-甲基吡唑-1-基）硼酸酯]和Tp（CONHt-Bu，Me）[三（3-叔丁基氨基羰基-5-甲基吡唑-1-基）硼酸酯]合成方法的改进。制备了它们的Tl（I）盐，即[三（3-苯胺羰基-5-甲基吡唑-1-基-κN(2)）硼酸根]铊（I），[Tl（C33H31BN9O3）]，（II），以及[三（3-叔丁基氨基羰基-5-甲基吡唑-1-基-κN(2)）硼酸根]铊（I），[Tl（C27H43BN9O3）]，（III），还有Cu（I）羰基配合物（Tp（CONHPh，Me））Cu（CO），即羰基[三（3-苯胺羰基-5-甲基吡唑-1-基-κN(2)）硼酸根]铜（I）四氢呋喃三溶剂合物，[Cu（C33H31BN9O3）（CO）]·3C4H8O，（IV），以及（Tp（CONHt-Bu，Me））Cu（CO），即羰基[三（3-叔丁基氨基羰基-5-甲基吡唑-1-基-κN(2)）硼酸根]铜（I）四氢呋喃半溶剂合物，[Cu（C27H43BN9O3）（CO）]·0.5C4H8O，（V）。将它们的光谱性质和结构与相关化合物进行了比较。（II）-（V）的分子通过酰胺基团与溶剂分子或相邻的配合物分子形成氢键。标题化合物具有与其他配体形成氢键的能力，并且表现出很强的吸电子特性。化合物（V）在晶体结构中显示出约800 Å(3)的空隙。
