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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis,Structures,and Properties of Peroxo and Superoxo Complexes
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Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis,Structures,and Properties of Peroxo and Superoxo Complexes

机译：具有脂肪族氮供体的四齿三脚形配体的铜（I）配合物的双氧反应性：过氧和超氧配合物的合成，结构和性质

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摘要

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-benzylamino-ethyl)amine (L~(H,Bn)),tris(N-benzyl-N-methylaminoethyl)amine (L~(Me,Bn)),or tris(N,N-dimethylaminoethyl)amine (L~(Me,Me)).All the copper(I) complexes reacted with dioxygen at low temperatures to produce superoxocopper(II) and/ or trans-(mu-l,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(L~(H,Bn))]~+ at -90 deg C in acetone resulted in the formation of a superoxo complex [Cu(L~(H,Bn))(O_2)]~+ as a less stable species and a peroxo complex [{Cu(L~(H,Bn))}_2(O_2)]~(2+) as a stable species.The structures of [Cu(L~(H,Bn))]ClO_4 and [{Cu(L~(H,Bn))}_2(O_2)(BPh_4)_2-8(CH_3)2CO were determined by X-ray crystallography.[{Cu(L~(H,Bn))}_2(O_2)]~(2+) has a trans-(mu-l,2-peroxo)-dicopper(II) core with a trigonal bipyramidal structure.The O-O bond distance is 1.450(5) A with an intermetallic Cu...Cu separation of 4.476(2) A.The resonance Raman spectrum of [{Cu(L~(H,Bn))}_2(O_2)]~(2+) measured at -90 deg C in acetone-d_6 showed abroad v(O-O) band at 837-834 cm~(-1) (788 cm~(-1) for an ~(18)O labeled sample) and two v(Cu-O) bands at 556 and 539 cm~(-1),suggesting the presence of two peroxo species in solution.[Cu(L~(Me,Bn))]~+ also produced both superoxo and trans-mu-1,2-peroxo species,[Cu(L~(Me,Bn))(O_2)]~+ and [{Cu(L~(Me,Bn))}_2(O_2)]~(2+).At a lower concentration of [Cu(L~(Me,Bn))]~+ (approx 0.24 mM) and higher dioxygen concentration (P(O_2)=approx 1 atm),the superoxo species is predominantly formed,whereas at a higher concentration of [Cu(L~(Me,Bn))]~+ (approx 1 mM) and lower dioxygen concentration (P(O_2)=approx 0.02 atm) the formation of the peroxo species is observed.The resonance Raman spectrum of [Cu(L~(Me,Bn))(O_2)]~+ (approx 1 mM) in acetone-d_6 at approx-95 deg C exhibited a v(O-O) band at 1120 cm~(-1) (1059 cm_(-1) for an ~(18)O labeled sample) and that of [{Cu(L~(Me,Bn))}_2(O_2)]~(2+) (approx 3 mM) in acetone-d_6 at approx 90 deg C showed two v(O-O) bands at 812 and 797 cm~(-1) (767 and 753 cm~(-1) for an ~(18)O labeled sample),respectively.A similar observation was also made for [{Cu(L~(Me,Me))}_2(O_2)]~(2+).Relationships between the energies of the LMCT and d-d transitions and those of the v(O-O) and v(Cu-O) stretching vibrations and the steric constraints in the Cu(II)-(O_2~(2-))-Cu(II) core are discussed.
机译：已经研究了用在末端氮上具有空间庞大取代基的三（氨基乙基）胺（叔戊）骨架构成的四齿三脚形配体（L）氧化铜（I），其中L =三（N-苄氨基-乙基）胺（L〜（H，Bn）），三（N-苄基-N-甲基氨基乙基）胺（L〜（Me，Bn））或三（N，N-二甲基氨基乙基）胺（L〜（Me，Me ）。所有铜（I）配合物在低温下都会与双氧反应生成超级氧铜（II）和/或反式（mu-1,2-过氧）-双铜（II）配合物，具体取决于末端的空间体积铜（I）络合物[Cu（L〜（H，Bn））]〜+在-90℃于丙酮中的反应导致形成超氧络合物[Cu（L〜（ H，Bn））（O_2）]〜+为不稳定物种，过氧化物配合物[{Cu（L〜（H，Bn））} _ 2（O_2）]〜（2+）为稳定物种。结构通过X射线晶体学测定[Cu（L〜（H，Bn））ClO_4和[{Cu（L〜（H，Bn））} _ 2（O_2）（BPh_4）_2-8（CH_3）2CO的含量。 [{Cu（L〜（H，Bn））} _ 2（O_2）]〜（2+）具有一个具有三角双锥体结构的反式（μ-1,2-过氧）-二铜（II）核.OO键距为1.450（5）A，金属间Cu ... Cu间距为4.476（2）A. [{Cu（L〜（H，Bn））} _ 2（O_2）]〜（2+）的共振拉曼光谱在丙酮-d_6中于-90℃测量，显示出837-834 cm〜处的v（OO）带。 （-1）（对于〜（18）O标记的样品为788 cm〜（-1））和556和539 cm〜（-1）处的两个v（Cu-O）谱带，建议在其中存在两种过氧化物。 [Cu（L〜（Me，Bn））] +也产生了超氧和反式mu-1,2-过氧物质，[Cu（L〜（Me，Bn））（O_2）] +和[{Cu（L〜（Me，Bn））} _ 2（O_2）]〜（2 +）。[Cu（L〜（Me，Bn））]〜+（约0.24 mM）和更高的浓度下当双氧浓度（P（O_2）=约1 atm）时，主要形成超氧物种，而较高浓度的[Cu（L〜（Me，Bn））]〜+（约1 mM）和较低的双氧浓度（ P（O_2）=约0.02 atm）观察到过氧化物的形成。[Cu（L〜（Me，Bn））（O_2）]〜+（约1 mM）的共振拉曼光谱丙酮-d_6中大约在95摄氏度时在1120 cm〜（-1）处出现av（OO）谱带（〜（18）O标记的样品在1059 cm _（-1）处）和[{Cu（L〜 （Me，Bn））} _ 2（O_2）]〜（2+）（约3 mM）在约90摄氏度的丙酮-d_6中显示两个v（OO）带，分别在812和797 cm〜（-1）（767） 〜（18）O标记的样品分别为753 cm〜（-1））。[{Cu（L〜（Me，Me））} _ 2（O_2）]〜（2+ LMCT和dd跃迁的能量与v（OO）和v（Cu-O）拉伸振动的能量与Cu（II）-（O_2〜（2-））-Cu中的空间约束之间的关系（二）核心讨论。

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