二氧锇（VI）卟啉对芳基肼的反应活性。肼基锇和氨基锇卟啉的分离。

Reactivity of dioxoosmium(VI) porphyrins toward arylhydrazine. Isolation of hydrazidoosmium and amidoosmium porphyrins.

作者信息

Leung Sarana Ka-Yan, Huang Jie-Sheng, Zhu Nianyong, Che Chi-Ming

机构信息

Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong.

出版信息

Inorg Chem. 2003 Nov 3;42(22):7266-72. doi: 10.1021/ic034389d.

DOI:10.1021/ic034389d

PMID:14577796

Abstract

Reactions of dioxoosmium(VI) porphyrins [Os(VI)(Por)O(2)] with excess 1,1-diphenylhydrazine in tetrahydrofuran at ca. 55 degrees C for 15 min afforded bis(hydrazido(1-))osmium(IV) porphyrins [Os(IV)(Por)(NHNPh(2))(2)] (1a, Por = TPP (meso-tetraphenylporphyrinato dianion); 1b, Por = TTP (meso-tetrakis(p-tolyl)porphyrinato dianion)), hydroxo(amido)osmium(IV) porphyrins [Os(IV)(Por)(NPh(2))(OH)] (2a, Por = TPP; 2b, Por = TTP), and bis(hydrazido(2-))osmium(VI) porphyrin [Os(VI)(Por)(NNPh(2))(2)] (3c, Por = TMP (meso-tetramesitylporphyrinato dianion)). The same reaction under harsher conditions (in refluxing tetrahydrofuran for ca. 1 h) gave a nitridoosmium(VI) porphyrin, [Os(VI)(Por)(N)(OH)] (4b, Por = TTP). Oxidation of 1a,b with bromine in dichloromethane afforded bis(hydrazido(2-)) complexes [Os(VI)(TPP)(NNPh(2))(2)] (3a) and [Os(VI)(TTP)(NNPh(2))(2)] (3b), respectively. All the new osmium porphyrins were identified by (1)H NMR, IR, and UV-vis spectroscopy and mass spectrometry; the structure of 2b was determined by X-ray crystallography (Os-NPh(2) = 1.944(6) A, Os-OH = 1.952(5) A).

摘要

二氧代锇（VI）卟啉[Os(VI)(Por)O₂]与过量的1,1 - 二苯基肼在四氢呋喃中于约55℃反应15分钟，得到双（肼基（1 - ））锇（IV）卟啉[Os(IV)(Por)(NHNPh₂)₂]（1a，Por = TPP（中 - 四苯基卟啉二价阴离子）；1b，Por = TTP（中 - 四（对甲苯基）卟啉二价阴离子））、羟基（酰胺基）锇（IV）卟啉[Os(IV)(Por)(NPh₂)(OH)]（2a，Por = TPP；2b，Por = TTP）以及双（肼基（2 - ））锇（VI）卟啉[Os(VI)(Por)(NNPh₂)₂]（3c，Por = TMP（中 - 四甲基卟啉二价阴离子））。在更苛刻的条件下（在回流的四氢呋喃中反应约1小时）进行相同反应，得到一种氮代锇（VI）卟啉，[Os(VI)(Por)(N)(OH)]（4b，Por = TTP）。在二氯甲烷中用溴氧化1a、b分别得到双（肼基（2 - ））配合物[Os(VI)(TPP)(NNPh₂)₂]（3a）和[Os(VI)(TTP)(NNPh₂)₂]（3b）。所有新的锇卟啉均通过¹H NMR、IR、UV - vis光谱和质谱进行鉴定；通过X射线晶体学确定了2b的结构（Os - NPh₂ = 1.944(6) Å，Os - OH = 1.952(5) Å）。