Spectrochemical series - spectrochemical series

Japanese: 分光化学系列 - ぶんこうかがくけいれつ(英語表記)spectrochemical series
Spectrochemical series - spectrochemical series

A scale used in the study of the structure and stability of complexes. It is also called the hypsochromic series. Many transition metal complexes have several absorption bands in the visible to ultraviolet range due to non-bonding d electrons. This means that many transition metal complexes have color, but the position of these absorption bands shifts when the ligands are changed, which is the reason for the diversity of colors in transition metal complexes. For example, the color of an aqueous solution of copper(II) sulfate is blue, and the color of an aqueous solution of nickel(II) sulfate is green, but when ammonia is added to them, they become deep blue-blue and wisteria, respectively. This is because the ligand of the aqua complex ion of copper(II) and nickel(II) (the ligand name for water is aqua) changes to ammonia (called ammine when it becomes a ligand), causing the position of the absorption band maximum to shift. Cobalt(III) complex salts that form complexes with various ligands are arranged by ligand from those with absorption maxima at short wavelengths to those with absorption maxima at long wavelengths as follows.

[In the case of cobalt(III) complex salts]
CN - >NO 2 - >SO 3 2- >2,2'-bipyridine, 1,10-phenanthroline >ethylenediamine >NH 3 >ONO - >NCS - >OH 2 >C 2 O 4 2- (bidentate) >NO 3 - ,SO 4 2- >OH - >CO 3 2- (bidentate) >CH 3 COO - >C 2 O 4 2- ,CO 3 2- (monodentate) >S 2 O 3 2- >F - >N 3 - >Cl - >CrO 4 2- >Br - >I -
This series is valid for all metal ions and represents an order of the strength of interactions with metal ions.

[Nakahara Katsunori]

Source: Shogakukan Encyclopedia Nipponica About Encyclopedia Nipponica Information | Legend

Japanese:

錯体の構造、安定度などの研究に用いられる尺度の一つ。浅色系列(せんしょくけいれつ)ともいう。多くの遷移金属錯体は、非結合性d電子が原因となって、可視部から紫外部にわたる領域にいくつかの吸収帯が存在する。このため多くの遷移金属錯体には色があることになるが、これらの吸収帯は配位子を変えるとその位置が移動し、遷移金属錯体の色の多様性の原因となっている。たとえば硫酸銅(Ⅱ)水溶液の色は青色、硫酸ニッケル(Ⅱ)水溶液の色は緑色であるが、これにアンモニアを加えると、それぞれ濃青藍(せいらん)色および藤(ふじ)色になる。これは銅(Ⅱ)およびニッケル(Ⅱ)のアクア錯イオンの配位子(水の配位子名はアクア)がアンモニア(配位子となるとアンミンという)に変わったため、吸収帯の極大位置が移動したためである。各種の多くの配位子の錯体をつくるコバルト(Ⅲ)錯塩で、吸収極大で短波長にあるものから、順次長波長にあるものへ配位子によって並べると以下のようになる。

〔コバルト(Ⅲ)錯塩の場合〕
CN->NO2->SO32->2,2'-ビピリジン,1,10-フェナントロリン>エチレンジアミン>NH3>ONO->NCS->OH2>C2O42-(二座)>NO3-,SO42->OH->CO32-(二座)>CH3COO->C2O42-,CO32-(単座)>S2O32->F->N3->Cl->CrO42->Br->I-
 この系列はすべての金属イオンに通用し、金属イオンに対する相互作用の強さの順序を表している。

[中原勝儼]

出典 小学館 日本大百科全書(ニッポニカ)日本大百科全書(ニッポニカ)について 情報 | 凡例

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