氮氧化物与（中-四苯基卟啉）钴（II）升华层的相互作用；氧从（硝基）卟啉钴（III）转移至游离一氧化氮的红外证据。

Interaction of nitrogen oxides with sublimed layers of (meso-tetraphenylporphyrinato)cobalt(II); IR evidence of oxo-transfer from (nitro)porphyrinatocobalt(III) to free nitric oxide.

作者信息

Kurtikyan Tigran S, Mardyukov Arthur N, Goodwin John A

机构信息

Molecular Structure Research Centre NAS, 375014 Yerevan, Armenia.

出版信息

Inorg Chem. 2003 Dec 15;42(25):8489-93. doi: 10.1021/ic0347844.

DOI:10.1021/ic0347844

PMID:14658904

Abstract

Interaction of a low-pressure NO2 with sublimed layers of (meso-tetraphenylporphyrinato)cobalt(II) (Co(TPP)) leads to formation of 5-coordinate nitro complex Co(III)(TPP)(NO2). Upon exposure of these layers to pyridine vapors, the fast reaction with formation of 6-coordinate nitro-pyridine porphyrins (Py)Co(III)(TPP)(NO2) occurs. By means of IR spectroscopy and use of nitrogen oxide isotopomers, it is shown that an oxo-transfer reaction occurs from 5-coordinate species to free nitric oxide (NO) while the 6-coordinate complex is rather inert. It is also demonstrated that the stepwise addition of low-pressure NO2 to nitrosyl complex Co(TPP)(NO) leads to formation of the nitro complex most likely by an exchange reaction.

摘要

低压二氧化氮与升华的（中-四苯基卟啉）钴（II）（Co（TPP））层相互作用会导致形成五配位硝基配合物Co（III）（TPP）（NO₂）。当这些层暴露于吡啶蒸气中时，会快速反应形成六配位硝基吡啶卟啉（Py）Co（III）（TPP）（NO₂）。通过红外光谱和使用氮氧化物同位素异构体表明，在六配位配合物相当惰性的情况下，从五配位物种到游离一氧化氮（NO）发生了氧转移反应。还证明了向亚硝酰基配合物Co（TPP）（NO）逐步添加低压二氧化氮最有可能通过交换反应导致硝基配合物的形成。