Chen Li, Yi Geun-Bae, Wang Li-Sheng, Dharmawardana Udeni R., Dart Amelia C., Khan Masood A., Richter-Addo George B.
Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, Oklahoma 73019.
Inorg Chem. 1998 Sep 7;37(18):4677-4688. doi: 10.1021/ic9801591.
Diethylnitrosamine reacts with [(TPP)Fe(THF)(2)]ClO(4) (TPP = 5,10,15,20-tetraphenylporphyrinato dianion) in toluene to generate the bis-nitrosamine complex, [(TPP)Fe(Et(2)NNO)(2)]ClO(4), in 96% isolated yield. The related [(TTP)Fe(Et(2)NNO)(2)]SbF(6) (TTP = 5,10,15,20-tetra-p-tolylporphyrinato dianion) complex is prepared in 70% isolated yield via a similar reaction in CH(2)Cl(2). Reaction of [(TPP)Fe(Et(2)NNO)(2)]ClO(4) in CH(2)Cl(2) with NO gas results in the displacement of one of the Et(2)NNO ligands to give the air-sensitive and thermally sensitive [(TPP)Fe(NO)(Et(2)NNO)]ClO(4) derivative. Reaction of (OEP)Ru(CO) (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion) with NOBF(4) in CH(2)Cl(2) gives [(OEP)Ru(NO)(H(2)O)]BF(4) as the final isolated product (after exposure to air) in 71% isolated yield. The aqua ligand is then displaced by Et(2)NNO in CH(2)Cl(2) to give [(OEP)Ru(NO)(Et(2)NNO)]BF(4) in 82% isolated yield. The valence isoelectronic (OEP)Ru(CO)(Et(2)NNO) compound is prepared in 71% isolated yield by the addition of excess Et(2)NNO to (OEP)Ru(CO) in CH(2)Cl(2). The nitrosyl amine complex [(OEP)Ru(NO)(HNEt(2))]BF(4) is prepared (i) in 78% yield by diethylamine addition to [(OEP)Ru(NO)(H(2)O)]BF(4) or (ii) in 71% isolated yield by diethylamine addition to [(OEP)Ru(NO)(Et(2)NNO)]BF(4). The osmium nitrosamine complexes, (TTP)Os(CO)(Et(2)NNO) and (OEP)Os(CO)(Et(2)NNO), are prepared in 74% and 66% yields, respectively, by diethylnitrosamine addition to the precursor (porphyrin)Os(CO) compounds in CH(2)Cl(2). The nitrosyl [(OEP)Os(NO)(Et(2)NNO)]BF(4) derivative is prepared in quantitative yield (by IR and (1)H NMR spectroscopy) by the reaction of (OEP)Os(CO)(Et(2)NNO) with NOBF(4). Labeling studies using (15)NOBF(4), Et(2)N(15)NO, and Et(2)NN(18)O have been used to assign the nitrosyl and nitrosamine bands in the IR spectra of several of the complexes. The solid-state structures of [(TPP)Fe(THF)(2)]ClO(4), [(TPP)Fe(Et(2)NNO)(2)]ClO(4), [(OEP)Ru(NO)(H(2)O)]BF(4), (OEP)Ru(CO)(Et(2)NNO), and (TTP)Os(CO)(Et(2)NNO) have also been determined by single-crystal X-ray diffraction. The Et(2)NNO ligands display a rare eta(1)-O binding mode in all three nitrosamine complexes.
二乙基亚硝胺与[(TPP)Fe(THF)(2)]ClO(4)（TPP = 5,10,15,20 - 四苯基卟啉二价阴离子）在甲苯中反应，生成双亚硝胺配合物[(TPP)Fe(Et(2)NNO)(2)]ClO(4)，分离产率为96%。相关的[(TTP)Fe(Et(2)NNO)(2)]SbF(6)（TTP = 5,10,15,20 - 四 - 对甲苯基卟啉二价阴离子）配合物通过在CH(2)Cl(2)中进行类似反应，以70%的分离产率制备。[(TPP)Fe(Et(2)NNO)(2)]ClO(4)在CH(2)Cl(2)中与NO气体反应，导致其中一个Et(2)NNO配体被取代，生成对空气和热敏感的[(TPP)Fe(NO)(Et(2)NNO)]ClO(4)衍生物。(OEP)Ru(CO)（OEP = 2,3,7,8,12,13,17,18 - 八乙基卟啉二价阴离子）与NOBF(4)在CH(2)Cl(2)中反应，得到[(OEP)Ru(NO)(H(2)O)]BF(4)作为最终分离产物（暴露于空气中后），分离产率为71%。然后在CH(2)Cl(2)中，水配体被Et(2)NNO取代，得到[(OEP)Ru(NO)(Et(2)NNO)]BF(4)，分离产率为82%。通过在CH(2)Cl(2)中向(OEP)Ru(CO)中加入过量的Et(2)NNO，以71%的分离产率制备了价电子等排体(OEP)Ru(CO)(Et(2)NNO)化合物。亚硝酰胺配合物[(OEP)Ru(NO)(HNEt(2))]BF(4)的制备方法如下：(i) 通过向[(OEP)Ru(NO)(H(2)O)]BF(4)中加入二乙胺，产率为78%；(ii) 通过向[(OEP)Ru(NO)(Et(2)NNO)]BF(4)中加入二乙胺，分离产率为71%。通过在CH(2)Cl(2)中向前体（卟啉）Os(CO)化合物中加入二乙基亚硝胺，分别以74%和66%的产率制备了锇亚硝胺配合物(TTP)Os(CO)(Et(2)NNO)和(OEP)Os(CO)(Et(2)NNO)。通过(OEP)Os(CO)(Et(2)NNO)与NOBF(4)反应，以定量产率（通过红外光谱和(1)H NMR光谱）制备了亚硝酰[(OEP)Os(NO)(Et(2)NNO)]BF(4)衍生物。使用(15)NOBF(4)、Et(2)N(15)NO和Et(2)NN(18)O进行的标记研究已用于确定几种配合物红外光谱中亚硝酰和亚硝胺谱带。[(TPP)Fe(THF)(2)]ClO(4)、[(TPP)Fe(Et(2)NNO)(2)]ClO(4)、[(OEP)Ru(NO)(H(2)O)]BF(4)、(OEP)Ru(CO)(Et(2)NNO)和(TTP)Os(CO)(Et(2)NNO)的固态结构也已通过单晶X射线衍射确定。在所有三种亚硝胺配合物中，Et(2)NNO配体呈现出罕见的η(1)-O配位模式。
