Hurtubise Venesia L, McArdle James M, Naeem Saira, Toscani Anita, White Andrew J P, Long Nicholas J, Wilton-Ely James D E T
Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, United Kingdom.
Inorg Chem. 2014 Nov 3;53(21):11740-8. doi: 10.1021/ic502015c. Epub 2014 Oct 13.
The new, unsymmetrical dithiocarbamate ligands, KS2CN(CH2CH═CH2)Me and KS2CN(CH2C≡CH)Me, are formed from the respective amines on reaction with KOH and carbon disulfide. The homoleptic complexes [Ni{S2CN(CH2CH═CH2)Me}2] and [M{S2CN(CH2C≡CH)Me}2] (M = Ni, Pd, Pt) are formed on reaction with suitable metal precursors. Conversion between the two pendant functionalities was confirmed by hydrogenation of [Ni{S2CN(CH2C≡CH)Me}2] to yield [Ni{S2CN(CH2CH═CH2)Me}2]. The monodithiocarbamate compounds of group 8, 10, and 11 metals, Ru{S2CN(CH2CH═CH2)Me}(dppm)2, [Ru(CH═CHC6H4Me-4){S2CN(CH2CH═CH2)Me}(CO)(PPh3)2], Ni{S2CN(CH2CH═CH2)Me}(dppp), and [Au{S2CN(CH2CH═CH2)Me}(PPh3)] were formed successfully. Using KS2CN(CH2C≡CH)Me, the complex Ru{S2CN(CH2C≡CH)Me}(dppm)2 was obtained from cis-[RuCl2(dppm)2]. One palladium example, Pd{S2CN(CH2C≡CH)Me}(PPh3)2, was also isolated in low yield. However, under the typical conditions employed, a rearrangement reaction prevented isolation of further group 10 propargyl-dithiocarbamate products. Over the extended reaction time required, Me(HC≡CCH2)NCS2(-) was found to undergo a remarkable, atom-efficient cyclization to form the thiazolidine-2-thione, H2C═CCH2N(Me)C(═S)S, in high yield, with MeC═CHN(Me)C(═S)S as the minor product. The reactivity of the pendant triple bonds in [Ni{S2CN(CH2C≡CH)Me}2] was probed in the reaction with [RuH(CO)(S2P(OEt)2)(PPh3)2] to form the trimetallic example [Ni{S2CN(Me)CH2CH═CHRu(CO)(S2P(OEt)2)(PPh3)2}2], while the copper(I) catalyzed reaction with benzylazide yielded the triazole product, [Ni{S2CN(Me)CH2(C2HN3)Bz}2]. KS2CN(CH2C≡CH)Me was also used to prepare the gold nanoparticles, Au@S2CN(CH2C≡CH)Me. Structural studies are reported for [Ru(CH═CHC6H4Me-4){S2CN(CH2CH═CH2)Me}(CO)(PPh3)2] and [Ru{S2CN(CH2C≡CH)Me}(dppm)2]PF6.
新型不对称二硫代氨基甲酸盐配体KS2CN(CH2CH═CH2)Me和KS2CN(CH2C≡CH)Me，是由相应的胺与氢氧化钾和二硫化碳反应形成的。与合适的金属前体反应可形成均配配合物[Ni{S2CN(CH2CH═CH2)Me}2]和[M{S2CN(CH2C≡CH)Me}2]（M = Ni、Pd、Pt）。通过将[Ni{S2CN(CH2C≡CH)Me}2]氢化生成[Ni{S2CN(CH2CH═CH2)Me}2]，证实了两种侧基官能团之间的转化。成功合成了第8、10和11族金属的单二硫代氨基甲酸盐化合物，Ru{S2CN(CH2CH═CH2)Me}(dppm)2、[Ru(CH═CHC6H4Me-4){S2CN(CH2CH═CH2)Me}(CO)(PPh3)2]、Ni{S2CN(CH2CH═CH2)Me}(dppp)和[Au{S2CN(CH2CH═CH2)Me}(PPh3)]。使用KS2CN(CH2C≡CH)Me，由顺式-[RuCl2(dppm)2]得到配合物Ru{S2CN(CH2C≡CH)Me}(dppm)2。还以低产率分离出了一个钯的例子，Pd{S2CN(CH2C≡CH)Me}(PPh3)2。然而在所采用的典型条件下，重排反应阻碍了进一步分离第10族炔丙基二硫代氨基甲酸盐产物。在所需的延长反应时间内，发现Me(HC≡CCH2)NCS2(-)发生了显著的、原子经济的环化反应，以高收率形成噻唑烷-2-硫酮H2C═CCH2N(Me)C(═S)S，以MeC═CHN(Me)C(═S)S作为次要产物。在与[RuH(CO)(S2P(OEt)2)(PPh3)2]反应中探究了[Ni{S2CN(CH2C≡CH)Me}2]中侧基三键的反应活性，形成了三金属实例[Ni{S2CN(Me)CH2CH═CHRu(CO)(S2P(OEt)2)(PPh3)2}2]，而铜(I)催化与苄基叠氮化物的反应生成了三唑产物[Ni{S2CN(Me)CH2(C2HN3)Bz}2]。KS2CN(CH2C≡CH)Me还用于制备金纳米颗粒Au@S2CN(CH2C≡CH)Me。报道了[Ru(CH═CHC6H4Me-4){S2CN(CH2CH═CH2)Me}(CO)(PPh3)2]和[Ru{S2CN(CH2C≡CH)Me}(dppm)2]PF6的结构研究。
