申请人:Schindler Siegfried
公开号:US20120016127A1
公开(公告)日:2012-01-19
The invention at hand describes Cu-(II)-oxygen adduct complexes, which are stable at room temperature, as well as methods for their production. In this, compounds of the general formula [L-Cu—O—O—Cu-L](BAr
4
)
2
are concerned. Here, BAr
4
−
is a tetraarylborate anion, selected from tetraphenylborate and tetrakis(3,5-trifluoromethyl)phenylborate. L represents a tripodal tetradentate ligand, wherein, each of the four binding sites of the tripodal tetradentate ligand is a nitrogen atom. Each of the three podal ligands is suitable for comprising an aliphatic amine or a nitrogen-containing heteroaromatic compound independently of one another. A bridge of one to four carbon atoms is located between the central nitrogen atom and the nitrogen atom of each of the podal ligands.
The Cu-(II)-oxygen adduct complexes according to the present invention are produced, by initially reacting the ligand L with a Cu-(I) salt to [Cu-L]X. Subsequently, the anion X of the Cu-(I) complex [Cu-L]X is replaced with tetraarylborate and the compound [Cu-L]BAr
4
obtained in this way is finally exposed to an oxygen-containing atmosphere. Hereby, [L-Cu—O—O—Cu-L](BAr
4
)
2
is formed.
The Cu-(II)-oxygen adduct complexes are suitable for being used as oxidation catalysts, for example for the oxidation of benzene to phenol or methane to methanol, for the oxidation of hydrogen, aromatic and aliphatic, saturated and unsaturated hydrocarbons, as well as alcohols and amines.
Furthermore, detection of the Cu-(II)-oxygen adduct complexes according to the present invention is suitable for being used for the detection of oxygen.
本发明描述了在室温下稳定的Cu-(II)-氧加合物配合物,以及它们的生产方法。在此,涉及到具有一般式[L-Cu—O—O—Cu-L](BAr4)2的化合物。这里,BAr4−是一种四芳基硼酸盐阴离子,可从四苯基硼酸盐和四(3,5-三氟甲基)苯基硼酸盐中选择。L代表一个三足四齿配体,其中,三足四齿配体的四个结合位点分别是氮原子。每个三足配体适合独立地包括脂肪胺或含氮杂环化合物。在中央氮原子和每个三足配体的氮原子之间有一个由一到四个碳原子组成的桥连接。根据本发明,Cu-(II)-氧加合物配合物是通过首先将配体L与Cu-(I)盐反应形成[Cu-L]X来生产的。随后,Cu-(I)配合物[Cu-L]X的阴离子X被四芳基硼酸盐取代,以此方式获得的化合物[Cu-L]BAr4最终暴露在含氧气氛中。这样,[L-Cu—O—O—Cu-L](BAr4)2就形成了。根据本发明,Cu-(II)-氧加合物配合物适用于用作氧化催化剂,例如用于苯氧化为苯酚或甲烷氧化为甲醇,以及氢氧化、芳香族和脂肪族、饱和和不饱和碳氢化合物、醇类和胺类的氧化。此外,根据本发明,检测Cu-(II)-氧加合物配合物适用于用于检测氧气。