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首页> 外文期刊>Zeitschrift fur Naturforschung, B. A Journal of Chemical Sciences >Syntheses, structures and vibrational spectroscopy of some mixed pyridine/triphenylphosphine adducts of copper(I) cyanide
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Syntheses, structures and vibrational spectroscopy of some mixed pyridine/triphenylphosphine adducts of copper(I) cyanide

机译:氰化铜(I)的某些吡啶/三苯基膦混合加合物的合成,结构和振动光谱

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摘要

Single crystal room temperature X-ray structure determinations are described for three adducts formed between copper(l) cyanide, pyridine ('py') and triphenylphosphine of (p : q : r =) 1: 1: 1, 1:1.5:0.5 and 1:0.5:2 (plus py hemisolvate) stoichiometry. The latter is binuclear [(Ph3P)(2)(py)Cu(muCN)Cu(PPh3)(2)(CN)]. py; the others are linear polymers with...Cu(mu-NC)Cu(mu-NC)Cu... spines with four-coordinate copper atoms, the coordination sphere of every copper atom in the first being completed by pendant py and Ph3P ligands, while the second has those of alternate copper atoms coordinated by a pair of py ligands. Assignment of bridging CN in all cases is crystallographically ambiguous. The IR spectra of the infinite polymeric complexes show bands that are assigned to vibrations of the CuCN chains in the complexes: v (CN), v (CuC/N) (the CuC/N stretching mode, involving vibration of the CN group between its two neighbouring Cu atoms), delta(CuCN) (the restricted rotation of the CN group) and delta(NCuC) (the counter vibration of the Cu substructure against the CN substructure). The v(CN) and v(CuC/N) frequencies show correlations with the Cu-C/N bond lengths that are similar in form to those recently established for a range of AgCN complexes.
机译:描述了氰化铜(l),吡啶('py')和三苯基膦(p:q:r =)1:1:1、1:1.5:0.5之间形成的三种加合物的单晶室温X射线结构测定和1:0.5:2(加上py半溶剂)化学计量。后者为双核[(Ph3P)(2)(py)Cu(muCN)Cu(PPh3)(2)(CN)]。 ;其他是具有...的Cu(mu-NC)Cu(mu-NC)Cu ...线形聚合物,带有四个配位的铜原子,第一个铜原子的配位球由py和Ph3P侧链完成配体,而第二个具有一对铜配体配位的交替铜原子。在所有情况下,桥接CN的分配在晶体学上都是模棱两可的。无限聚合配合物的红外光谱显示出与配合物中CuCN链的振动相关的谱带:v(CN),v(CuC / N)(CuC / N拉伸模式,涉及其之间的CN基团的振动两个相邻的Cu原子),delta(CuCN)(CN基团的受限旋转)和delta(NCuC)(Cu子结构相对于CN子结构的反向振动)。 v(CN)和v(CuC / N)频率显示与Cu-C / N键长的相关性,其形式与最近为一系列AgCN配合物建立的键长相似。

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