Hydroxylation of a methyl group:: synthesis of [Cu2(btmmO)2I]+ and of [Cu2(btmmO)2]2+ containing the novel ligand {bis(trimethylmethoxy)guanidino} propane (btmmO) by copper-assisted oxygen activation
Hydroxylation of a methyl group:: synthesis of [Cu2(btmmO)2I]+ and of [Cu2(btmmO)2]2+ containing the novel ligand {bis(trimethylmethoxy)guanidino} propane (btmmO) by copper-assisted oxygen activation
复制标题
DOI：
10.1016/j.ica.2004.10.009
复制
发表时间：
2005-03-01
影响因子：
2.8
通讯作者：
Henkel, G
中科院分区：
文献类型：
--
作者：
Herres, S;Heuwing, AJ;Henkel, G
双胍铜（I）化合物[Cu（btmgp）I]和[Cu-2（btmgp）（2）][PF_6]（2）与分子氧在低温下反应得到含有双-μ-氧代二铜（III）核的配合物，其能够羟基化{双（四甲基）胍基}丙烷配体的一个N-CH_3-基团。新的配体{双（三甲基甲氧基）胍基}丙烷（btmmO）的形成被报道，因为它代表了第一个羟基化的N-甲基。该反应的产物是新型的烷氧桥联双核铜配合物，即以新型桥联方式含有碘离子的[Cu-2（btmmO）（2）I]（+），以及已在其配合物盐[Cu-2（btmmO）（2）I]I（.）1/2C2H5OH和[Cu-2（btmmO）（2）][PF 6]（2）（.）2-MeCN。同时，羟基桥联的双核铜化合物[Cu-2（btmgp）（2）（mu-OH）（2）]I-2和[Cu-2（btmgp）（2）（mu-OH）（2）][PF 6]（2）作为偶联产物形成。的双-mu-oxodicopper（III）配合物的形成进行了监测，通过UV/VIS光谱，和反应产物的特征在于通过X-射线衍射，振动光谱和元素分析。(c)2004 Elsevier B. V.保留所有权利。
The reaction of the bisguanidine copper(I) compounds [Cu(btmgp)I] and [Cu-2(btmgp)(2)][PF6](2) with molecular oxygen afforded at low temperatures complexes containing the bis-mu-oxo dicopper(III) core, which is capable to hydroxylate one of the N-CH3-groups of the {bis(tetramethyl)guanidino} propane ligands. The formation of the novel ligand {bis(trimethylmethoxy)guanidino} propane (btmmO) is reported as it represents the first hydroxylation of a N-methyl group. The products of this reaction are novel alkoxo-bridged binuclear copper complexes, namely [Cu-2(btmmO)(2)I](+) containing an iodide ion in a novel bridging situation, as well as [Cu-2(btmmO)(2)](2+) which have been identified in their complex salts [Cu-2(btmmO)(2)I]I(.)1/2 C2H5OH and [Cu-2(btmmO)(2)][PF6](2)(.)2-MeCN, respectively. Concomitantly, the hydroxo-bridged binuclear copper compounds [Cu-2(btmgp)(2)(mu-OH)(2)]I-2 and [Cu-2(btmgp)(2)(mu-OH)(2)][PF6](2) are formed as couple products. The formation of the bis-mu-oxodicopper(III) complexes was monitored by UV/Vis-spectroscopy, and the reaction products were characterised by X-ray diffraction, vibrational spectroscopy and elemental analysis. (c) 2004 Elsevier B.V. All rights reserved.