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双-[8-(二甲基膦基)喹啉]-镍(II)和-铂(II)络合阳离子的分子结构比较。

Comparison of mol-ecular structures of -bis-[8-(di-methyl-phosphan-yl)quinoline]-nickel(II) and -platinum(II) complex cations.

作者信息

Mori Masatoshi, Suzuki Takayoshi

机构信息

Graduate School of Natural Science and Technology, Okayama University, Okayama, 700-8530, Japan.

Research Institute for Interdisciplinary Science, Okayama University, Okayama, 700-8530, Japan.

出版信息

Acta Crystallogr E Crystallogr Commun. 2020 Nov 6;76(Pt 12):1813-1817. doi: 10.1107/S2056989020014437. eCollection 2020 Dec 1.

Abstract

The crystal structures of the complexes (-4-2)--bis-[8-(di-methyl-phosphan-yl)quinoline-κ ,]nickel(II) bis-(perchlorate) nitro-methane monosolvate, Ni(CHNP)·CHNO (), and (-4-2)--bis-[8-(di-methyl-phos-phan-yl)quinoline-κ ,]platinum(II) bis-(tetra-fluoro-borate) aceto-nitrile monosolvate, Pt(CHNP)·CHN (), are reported. In both complex cations, two phosphanyl-quinolines act as bidentate -donating chelate ligands and form the mutually configuration in the square-planar coordination geometry. The strong influence of the di-methyl-phosphanyl donor group is confirmed by the Ni-N bond lengths in , 1.970 (2) and 1.982 (2) Å and, the Pt-N bond lengths of , 2.123 (4) and 2.132 (4) Å, which are relatively long as compared to those in the analogous 8-(di-phenyl-phosphan-yl)quinoline complexes. Mutually -positioned quinoline donor groups would give a severe steric hindrance between their -H atoms. In order to reduce such a steric congestion, the Ni complex in shows a tetra-hedral distortion of the coordination geometry, as parameterized by τ = 0.199 (1)°, while the Pt complex in exhibits a typical square-planar coordination geometry [τ = 0.014 (1)°] with a large bending deformation of the ideally planar MePqn chelate planes. In the crystal structure of , three F atoms of one of the BF anions are disordered over two sets of positions with refined occupancies of 0.573 (10) and 0.427 (10).

摘要

报道了配合物(-4-2)-双-[8-(二甲基膦基)喹啉-κ,]镍(II)双(高氯酸盐)硝基甲烷单溶剂合物Ni(CHNP)·CHNO ()和(-4-2)-双-[8-(二甲基膦基)喹啉-κ,]铂(II)双(四氟硼酸盐)乙腈单溶剂合物Pt(CHNP)·CHN ()的晶体结构。在这两种配合物阳离子中,两个膦基喹啉作为双齿 - 供体螯合配体,并在平面正方形配位几何构型中形成相互 构型。二甲基膦基供体基团的强烈 影响通过 中Ni-N键长1.970 (2)和1.982 (2) Å以及 中Pt-N键长2.123 (4)和2.132 (4) Å得到证实,与类似的8-(二苯基膦基)喹啉配合物相比,这些键长相对较长。相互定位的喹啉供体基团在它们的 -H原子之间会产生严重的空间位阻。为了减少这种空间拥挤, 中的Ni配合物表现出配位几何构型的四面体畸变,参数τ = 0.199 (1)°,而 中的Pt配合物表现出典型的平面正方形配位几何构型[τ = 0.014 (1)°],理想平面的MePqn螯合平面有较大的弯曲变形。在 的晶体结构中,一个BF 阴离子的三个F原子在两组位置上无序分布,精修占有率为0.573 (10)和0.427 (10)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/197a/7784645/e96d7e599a55/e-76-01813-fig1.jpg

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