Chesman Anthony S R, Turner David R, Deacon Glen B, Batten Stuart R
School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
Chem Asian J. 2009 May 4;4(5):761-9. doi: 10.1002/asia.200800323.
The metal-promoted nucleophilic addition of diaminoalkanes to dicyanonitrosomethanide, C(CN)2(NO)- (dcnm), and subsequent cyclization has been utilized in the synthesis of novel anionic species. The addition and cyclization of 1,2-diaminoethane (en) to both nitrile groups of dcnm forms the anion diimidazolinylnitrosomethanide (dinm), isolated in the dinuclear complex [{Cu(dinm)(en)}2en][ClO4]2 (1). The same reaction solution yields [Cu(cinm)(ainm)] (cinm=cyanoimidazolinylnitrosomethanide, ainm=(((2-aminoethyl)amino)iminomethyl)imidazolinylnitrosomethanide) (2), which contains intermediates of the dinm species, supporting a stepwise mechanism of addition of the diamine followed by cyclization. 1,3-Diaminopropane (pn) added and cyclized on only one nitrile group to form a 1,4,5,6-tetrahydropyrimidine ring. This resulted in the formation of the cyanonitroso-1,4,5,6-tetrahydropyrimidinylmethanide ligand (cnpm) in complexes with the general formula [M(cnpm)2(pn)] (M=Cu (3a), Ni (3b), Zn (3c)). These reactions are contrasted to the addition of ethanolamine in the pyridine (py) complex [Ni(chnm)2(py)2].(py) (4) (chnm=cyano((2-hydroxyethyl)amino)iminomethylnitrosomethanide) with no cyclization, demonstrating the higher reactivity of amines compared with alcohols. The formation of the complexes [M(cmnm)2(mame)] (M=Co (5a), Ni (5b), cmnm=cyano(imino(methoxy)methyl)nitrosomethanide, mame=1-dimethylamino-2-methylaminoethane) indicate mame may be too sterically hindered to add to dcnm under similar reaction conditions.
二氨基烷烃与二氰基亚硝基甲烷（C(CN)₂(NO)⁻，简称dcnm）在金属促进下发生亲核加成反应，随后进行环化反应，已被用于合成新型阴离子物种。1,2 - 二氨基乙烷（en）与dcnm的两个腈基发生加成和环化反应，形成阴离子二咪唑啉基亚硝基甲烷（dinm），该阴离子存在于双核配合物[{Cu(dinm)(en)}₂en][ClO₄]₂（1）中。相同的反应溶液生成[Cu(cinm)(ainm)]（cinm = 氰基咪唑啉基亚硝基甲烷，ainm = （（（2 - 氨基乙基）氨基）亚氨基甲基）咪唑啉基亚硝基甲烷）（2），其中含有dinm物种的中间体，这支持了二胺先加成后环化的分步反应机理。1,3 - 二氨基丙烷（pn）仅在一个腈基上发生加成和环化反应，形成一个1,4,5,6 - 四氢嘧啶环。这导致在通式为[M(cnpm)₂(pn)]（M = Cu （3a），Ni （3b），Zn （3c））的配合物中形成氰基亚硝基 - 1,4,5,6 - 四氢嘧啶基甲烷配体（cnpm）。这些反应与乙醇胺在吡啶（py）配合物[Ni(chnm)₂(py)₂]·(py)（4）（chnm = 氰基（（2 - 羟乙基）氨基）亚氨基甲基亚硝基甲烷）中的加成反应形成对比，该反应未发生环化，表明胺类与醇类相比具有更高的反应活性。配合物[M(cmnm)₂(mame)]（M = Co （5a），Ni （5b），cmnm = 氰基（亚氨基（甲氧基）甲基）亚硝基甲烷，mame = 1 - 二甲基氨基 - 2 - 甲基氨基乙烷）的形成表明，在类似反应条件下，mame可能由于空间位阻过大而无法加成到dcnm上。
