Syntheses, characterization, and catalytic ability in alkane oxygenation of chloro(dimethyl sulfoxide)ruthenium(II) complexes with tris(2-pyridylmethyl)amine and its derivatives
Syntheses, characterization, and catalytic ability in alkane oxygenation of chloro(dimethyl sulfoxide)ruthenium(II) complexes with tris(2-pyridylmethyl)amine and its derivatives
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DOI：
10.1021/ic060722c
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发表时间：
2006-10-02
影响因子：
4.6
通讯作者：
Yamagishi, Takamichi
中科院分区：
文献类型：
--
作者：
Yamaguchi, Motowo;Kousaka, Hiroyuki;Yamagishi, Takamichi
已经制备了具有四齿配体如三（2-吡啶基甲基）胺（TPA）、三[2-（5-甲氧羰基）吡啶基甲基]胺[5-（MeOCO）（3）-TPA]、三（2-喹啉基甲基）胺（TQA）或双（2-吡啶基甲基）甘氨酸酯（BPG）的新的钌（II）配合物。该配体与[RuCl_2（Me_2SO_4）]反应生成了含有TPA或BPG的氯代（二甲基亚砜-kS）钌（II）配合物的反式和顺式异构体的混合物，而5-（MeOCO）（3）-TPA和TQA则选择性地得到了反式（Cl，N-氨基）异构体。[RuCl（TPA）（Me_2SO）]（+）配合物的顺、反异构体可通过分级重结晶分离。用X-射线衍射法测定了反式、顺式（Cl，N-氨基）-[RuCl（TPA）（Me_2SO）]（+）配合物和反式（Cl，N-氨基）-[RuCl{5-（MeOCO）（3）-TPA}（Me_2SO）]（+）配合物的分子结构。TPA与[RuCl_2（PhCN）（4）]反应得到单一的氯代苄腈钌（II）配合物，而与BPG反应得到双苄腈钌（II）配合物。顺式（Cl，N-氨基）-[RuCl（TPA）（Me 2SO）]（+）络合物在热力学上比反式异构体稳定得多，并且在65 - 100 ℃下在二甲基亚砜中异构化。这些钌（II）配合物催化的烷烃的氧化反应进行了研究。以间氯过苯甲酸为助氧化剂，合成了氯代（二甲基亚砜-kS）钌（II）与TPA及其衍生物的配合物，并对其催化性能进行了研究。金刚烷被有效地选择性氧化成1-金刚烷醇，产率高达88%。在所考察的配合物中，氯代（二甲基亚砜-kS）钌（II）与5-（MeOCO）（3）-TPA的配合物是活性最高的催化剂。
New ruthenium(II) complexes having a tetradentate ligand such as tris(2-pyridylmethyl) amine (TPA), tris[2-(5-methoxycarbonyl) pyridylmethyl] amine [5-(MeOCO)(3)-TPA], tris(2-quinolylmethyl) amine (TQA), or bis(2-pyridylmethyl)glycinate (BPG) have been prepared. The reaction of the ligand with [RuCl2(Me2SO4] resulted in a mixture of trans and cis isomers of the chloro(dimethyl sulfoxide-kS) ruthenium(II) complexes containing a TPA or a BPG, whereas a trans(Cl, N-amino) isomer was selectively obtained for 5-( MeOCO)(3)-TPA and TQA. The trans and cis isomers of the [RuCl(TPA)(Me2SO)](+) complex were easily separated by fractional recrystallization. The molecular structures of trans- and cis(Cl,N-amino)-[RuCl(TPA)(Me2SO)](+) complexes and the trans(Cl, N-amino)-[RuCl{5-(MeOCO)(3)-TPA}(Me2SO)](+) complex have been determined by X-ray structural analyses. The reaction of TPA with [RuCl2(PhCN)(4)] gave a single isomer of the chloro(benzonitrile) ruthenium(II) complex, whereas the bis(benzonitrile) ruthenium(II) complex was obtained with BPG. The cis(Cl, N-amino)-[RuCl(TPA)(Me2SO)](+) complex is thermodynamically much less stable than the trans isomer and isomerizes in dimethyl sulfoxide at 65 - 100 degrees C. Oxygenation of alkanes catalyzed by these ruthenium(II) complexes has been examined. The chloro(dimethyl sulfoxide-kS) ruthenium(II) complexes with TPA and its derivatives using m-chloroperbenzoic acid as a cooxidant showed high catalytic ability. Adamantane was efficiently and selectively oxidized to give 1-adamantanol up to 88%. The chloro(dimethylsulfoxide-kS)ruthenium(II) complex with 5-(MeOCO)(3)-TPA was found to be the most active catalyst among the complexes examined.