Comparison of two Mn IV Mn IV -bis-μ-oxo complexes {[Mn IV (N 4 (6-Me-DPEN))] 2 (μ-O) 2 } 2+ and {[Mn IV (N 4 (6-Me-DPPN))] 2 (μ-O) 2 } 2+
Comparison of two Mn IV Mn IV -bis-μ-oxo complexes {[Mn IV (N 4 (6-Me-DPEN))] 2 (μ-O) 2 } 2+ and {[Mn IV (N 4 (6-Me-DPPN))] 2 (μ-O) 2 } 2+
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两种 Mn IV Mn IV -双-μ-氧配合物 {[Mn IV (N 4 (6-Me-DPEN))] 2 (μ-O) 2 } 2 和 {[Mn IV (N 4 (6-
DOI：
10.1107/s2056989020004557
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Kovacs, Julie A.
中科院分区：
文献类型：
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作者：
Coggins, Michael K.;Downing, Alexandra N.;Kaminsky, Werner;Kovacs, Julie A.
将叔丁基过氧化氢（tBuOOH）加成到两种结构相关的含有N，N-双（6-甲基-2-吡啶甲基）乙烷-1，2-二胺（6-Me-DPEN）和N，N-双（6-甲基-2-吡啶基甲基）丙烷-1，2-二胺（6-Me-DPPN）导致形成高价双氧代络合物，即二-μ-氧化-双{[N，N-双（6-甲基-2-吡啶基甲基）乙烷-1，2-二胺]锰（II）}（Mn-Mn）bis（四苯基硼酸盐）二水合物，[Mn（C16 H22 N4）2 O2]（C24 H20 B）2·2 H2O或{[MnIV（N4（6-Me-DPEN））]2（μ-O）2}（2BPh 4）（2 H2O）（1）和二-μ-氧化-双{[N，N-bis（6-甲基-2-吡啶甲基）丙烷-1，3-二胺]锰（II）}（Mn-Mn）双[Mn（C17H24N4）2O2]（C24H20B）2·2C4H10O或{[MnIV（N4（6-MeDPPN））]2（μ-O）2}（2BPh4）（2Et2O）（2）。络合物1和2都含有以前在铁、铜和锰的高价双氧化合物中发现的“金刚石核”基序。与1中的乙基接头的柔性相比，2的配体支架中的丙基接头的柔性导致更长的Mn-N键，如人们所预期的。Mn-Mn距离和Mn-O键长支持1和2中锰离子的MnIV氧化态归属。Mn中心周围的角度与局部伪八面体几何形状一致。
The addition of tert-butyl hydroperoxide (tBuOOH) to two structurally related MnII complexes containing N,N-bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me-DPEN) and N,N-bis(6-methyl-2-pyridylmethyl)propane-1,2-diamine (6-Me-DPPN) results in the formation of high-valent bis-oxo complexes, namely di-μ-oxido-bis{[N,N-bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine]manganese(II)}(Mn—Mn) bis(tetraphenylborate) dihydrate, [Mn(C16H22N4)2O2](C24H20B)2·2H2O or {[MnIV(N4(6-Me-DPEN))]2(μ-O)2}(2BPh4)(2H2O) (1) and di-μ-oxido-bis{[N,N-bis(6-methyl-2-pyridylmethyl)propane-1,3-diamine]manganese(II)}(Mn—Mn) bis(tetraphenylborate) diethyl ether disolvate, [Mn(C17H24N4)2O2](C24H20B)2·2C4H10O or {[MnIV(N4(6-MeDPPN))]2(μ-O)2}(2BPh4)(2Et2O) (2). Complexes 1 and 2 both contain the `diamond core' motif found previously in a number of iron, copper, and manganese high-valent bis-oxo compounds. The flexibility in the propyl linker in the ligand scaffold of 2, as compared to that of the ethyl linker in 1, results in more elongated Mn—N bonds, as one would expect. The Mn—Mn distances and Mn—O bond lengths support an MnIV oxidation state assignment for the Mn ions in both 1 and 2. The angles around the Mn centers are consistent with the local pseudo-octahedral geometry.