The first platinum(IV) complexes with glucopyranoside ligands. A new coordination mode of carbohydrates
The first platinum(IV) complexes with glucopyranoside ligands. A new coordination mode of carbohydrates
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DOI：
10.1021/ic9801692
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发表时间：
1998-09-07
影响因子：
4.6
通讯作者：
Steinborn, D
中科院分区：
文献类型：
--
作者：
Junicke, H;Bruhn, C;Steinborn, D
[（PtMe 3 I）（4）]与AgBF 4在丙酮中反应，得到fac-[PtMe 3（Me 2CO）（3）] BF 4（2），其分离为强水分和空气敏感的无色晶体，并通过微量分析和NMR光谱（H-1，C-13，Pt-195）表征。X射线结构分析（正交晶系，Pcab，a = 15.599（3）埃，B = 15.685（2）埃，c = 15.763（3）埃，Z = 8）表明2是单体，阳离子表现出局部C-3向上对称性。2与吡喃葡萄糖（1，6-脱水-β-D-吡喃葡萄糖（3a）、1-甲基-α-D-吡喃葡萄糖苷（3b）和1-苯基-β-D-吡喃葡萄糖苷（3c））反应生成碳水化合物络合物[PtMe 3L] BF 4（4a-4c，L = 3a-3c）。通过微量分析、ESI质谱和NMR光谱（H-1、C-13、Pt-195）对复合物进行了表征，表明碳水化合物充当由羟基2-OH和4-OH以及由吡喃糖环的缩醛氧原子配位的三齿螯合配体。该结构也通过4a（斜方晶系，P2（1）2（1）2（1），a = 6.404（1）埃，B = 8.636（2）埃，27.161（5）埃，Z = 4）的X射线结构分析来确认。两个五元环和一个六元环的1，3，2-二氧杂铂环的环状体系并非没有角应变;两个O-Pt-O角明显小于90度（O2-Pt-O 5 73.6（2），O 4-Pt-O 5 75.6（2）度）。与吡喃糖环中的缩醛氧原子连接的Pt-O键（Pt-O 5 2.288（5）埃）明显长于两个Pt-OH键（Pt-O2 2.246（5），Pt-O 4 2.248（4）），并且属于最长的Pt-O键。
[(PtMe3I)(4)] reacts with AgBF4 in acetone to give fac-[PtMe3(Me2CO)(3)]BF4 (2) which was isolated as strongly moisture and air sensitive, colorless crystals and characterized by microanalysis and NMR spectroscopy (H-1, C-13, Pt-195). The X-ray structure analysis (orthorhombic, Pcab, a = 15.599(3) Angstrom, b = 15.685(2) Angstrom, c = 15.763(3) Angstrom, Z = 8) reveals that 2 is monomeric and that the cation exhibits local C-3 upsilon, symmetry. The reaction of 2 with glucopyranoses (1,6-anhydro-beta-D-glucopyranose (3a), 1-methyl-alpha-D-glucopyranoside (3b), and 1-phenyl-beta-D-glucopyranoside (3c)) yields carbohydrate complexes [PtMe3L]BF4 (4a-4c, L = 3a-3c). The complexes were characterized by microanalysis, ESI mass spectrometry and by NMR spectroscopy (H-1, C-13, Pt-195) displaying that the carbohydrates act as tridentate chelating ligands coordinated by the hydroxyl groups 2-OH and 4-OH and by the acetal oxygen atom of the pyranose ring. This structure was also confirmed by X-ray structure analysis of 4a (orthorhombic, P2(1)2(1)2(1), a = 6.404(1) Angstrom, b = 8.636(2) Angstrom, 27.161(5) Angstrom, Z = 4). The cyclic system of the two five-membered and the one six-membered 1,3,2-dioxaplatina rings is not free from angle strain; two O-Pt-O angles are distinctly smaller than 90 degrees (O2-Pt-O5 73.6(2), O4-Pt-O5 75.6(2)degrees). The Pt-O bond to the acetal oxygen atom in the pyranose ring is significantly longer (Pt-O5 2.288(5) Angstrom) than the two Pt-OH bonds (Pt-O2 2.246(5), Pt-O4 2.248(4) and belongs to the longest Pt-O bonds at all.