| Item type |
学術雑誌論文 / Journal Article(1) |
| 公開日 |
2017-10-03 |
| タイトル |
|
|
タイトル |
Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes |
|
言語 |
en |
| 言語 |
|
|
言語 |
eng |
| 資源タイプ |
|
|
資源タイプ識別子 |
http://purl.org/coar/resource_type/c_6501 |
|
資源タイプ |
journal article |
| ID登録 |
|
|
ID登録 |
10.24517/00010728 |
|
ID登録タイプ |
JaLC |
| 著者 |
Komiyama, Kazuya
Furutachi, Hideki
Nagatomo, Shigenori
Hashimoto, Akifumi
Hayashi, Hideki
Fujinami, Shuhei
Suzuki, Masatatsu
Kitagawa, Teizo
|
| 著者別表示 |
古舘, 英樹
藤波, 修平
鈴木, 正樹
|
| 書誌情報 |
Bulletin of the Chemical Society of Japan
巻 77,
号 1,
p. 59-72,
発行日 2004-01-01
|
| ISSN |
|
|
収録物識別子タイプ |
ISSN |
|
収録物識別子 |
0009-2673 |
| NCID |
|
|
収録物識別子タイプ |
NCID |
|
収録物識別子 |
AA00580132 |
| 出版者 |
|
|
出版者 |
The Chemical Society of Japan = 日本化学会 |
| 抄録 |
|
|
内容記述タイプ |
Abstract |
|
内容記述 |
Oxygenation of copper(I) with tetradentate tripodal ligands (L) comprised of a tris(aminoethyl)amine (tren) skeleton having sterically bulky substituent(s) on the terminal nitrogens has been investigated, where L = tris(N-benzylaminoethyl)amine (LH,Bn), tris(N-benzyl-N-methylaminoethyl)amine (LMe,Bn), or tris(N,N-dimethylaminoethyl)amine (LMe,Me). All the copper(I) complexes reacted with dioxygen at low temperatures to produce superoxocopper(II) and/or trans-(μ-1,2-peroxo)-dicopper(II) complexes depending on the steric bulkiness of the terminal nitrogens and the reaction conditions. The reaction of a copper(I) complex [Cu(LH,Bn)]+ at −90 °C in acetone resulted in the formation of a superoxo complex [Cu(LH,Bn)(O2)]+ as a less stable species and a peroxo complex [{Cu(LH,Bn)}2(O2)]2+ as a stable species. The structures of [Cu(LH,Bn)]ClO4 and [{Cu(LH,Bn)}2(O2)](BPh4)2·8(CH3)2CO were determined by X-ray crystallography. [{Cu(LH,Bn)}2(O2)]2+ has a trans-(μ-1,2-peroxo)-dicopper(II) core with a trigonal bipyramidal structure. The O–O bond distance is 1.450(5) Å with an intermetallic Cu···Cu separation of 4.476(2) Å. The resonance Raman spectrum of [{Cu(LH,Bn)}2(O2)]2+ measured at −90 °C in acetone-d6 showed a broad ν(O–O) band at 837–834 cm−1 (788 cm−1 for an 18O labeled sample) and two ν(Cu–O) bands at 556 and 539 cm−1, suggesting the presence of two peroxo species in solution. [Cu(LMe,Bn)]+ also produced both superoxo and trans-μ-1,2-peroxo species, [Cu(LMe,Bn)(O2)]+ and [{Cu(LMe,Bn)}2(O2)]2+. At a lower concentration of [Cu(LMe,Bn)]+ (∼0.24 mM) and higher dioxygen concentration (P(O2) = ∼1 atm), the superoxo species is predominantly formed, whereas at a higher concentration of [Cu(LMe,Bn)]+ (∼1 mM) and lower dioxygen concentration (P(O2) = ∼0.02 atm) the formation of the peroxo species is observed. The resonance Raman spectrum of [Cu(LMe,Bn)(O2)]+ (∼1 mM) in acetone-d6 at ∼−95 °C exhibited a ν(O–O) band at 1120 cm−1 (1059 cm−1 for an 18O labeled sample) and that of [{Cu(LMe,Bn)}2(O2)]2+ (∼3 mM) in acetone-d6 at ∼−90 °C showed two ν(O–O) bands at 812 and 797 cm−1 (767 and 753 cm−1 for an 18O labeled sample), respectively. A similar observation was also made for [{Cu(LMe,Me)}2(O2)]2+. Relationships between the energies of the LMCT and d–d transitions and those of the ν(O–O) and ν(Cu–O) stretching vibrations and the steric constraints in the Cu(II)–(O22−)–Cu(II) core are discussed. |
| 権利 |
|
|
権利情報 |
Copyright © The Chemical Society of Japan 日本化学会 |
| 著者版フラグ |
|
|
出版タイプ |
VoR |
|
出版タイプResource |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| 関連URI |
|
|
関連タイプ |
isVersionOf |
|
|
識別子タイプ |
DOI |
|
|
関連識別子 |
https://doi.org/10.1246/bcsj.77.59 |
| 関連URI |
|
|
関連タイプ |
isIdenticalTo |
|
|
識別子タイプ |
URI |
|
|
関連識別子 |
https://www.jstage.jst.go.jp/browse/bcsj |
| 関連URI |
|
|
関連タイプ |
isIdenticalTo |
|
|
識別子タイプ |
URI |
|
|
関連識別子 |
http://www.chemistry.or.jp/ |
SC-PR-SUZUKI-M-59.pdf (510.7 kB)
.png)
