Multimetallic Complexes and Functionalized Nanoparticles Based on Unsymmetrical Dithiocarbamate Ligands with Allyl and Propargyl Functionality

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• 作者：Venesia L. Hurtubise ; James M. McArdle ; Saira Naeem ; Anita Toscani ; Andrew J. P. White ; Nicholas J. Long ; James D. E. T. Wilton-Ely
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 3, 2014
• 年：2014
• 卷：53
• 期：21
• 页码：11740-11748
• 全文大小：503K
• ISSN：1520-510X

文摘

The new, unsymmetrical dithiocarbamate ligands, KS₂CN(CH₂CH鈺怌H₂)Me and KS₂CN(CH₂C鈮H)Me, are formed from the respective amines on reaction with KOH and carbon disulfide. The homoleptic complexes [Ni{S₂CN(CH₂CH鈺怌H₂)Me}₂] and [M{S₂CN(CH₂C鈮H)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鈮H)Me}₂] to yield [Ni{S₂CN(CH₂CH鈺怌H₂)Me}₂]. The monodithiocarbamate compounds of group 8, 10, and 11 metals, [Ru{S₂CN(CH₂CH鈺怌H₂)Me}(dppm)₂]⁺, [Ru(CH鈺怌HC₆H₄Me-4){S₂CN(CH₂CH鈺怌H₂)Me}(CO)(PPh₃)₂], [Ni{S₂CN(CH₂CH鈺怌H₂)Me}(dppp)]⁺, and [Au{S₂CN(CH₂CH鈺怌H₂)Me}(PPh₃)] were formed successfully. Using KS₂CN(CH₂C鈮H)Me, the complex [Ru{S₂CN(CH₂C鈮H)Me}(dppm)₂]⁺ was obtained from cis-[RuCl₂(dppm)₂]. One palladium example, [Pd{S₂CN(CH₂C鈮H)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鈮CH₂)NCS₂^{鈥?/sup> was found to undergo a remarkable, atom-efficient cyclization to form the thiazolidine-2-thione, H₂C鈺怌CH₂N(Me)C(鈺怱)S, in high yield, with MeC鈺怌HN(Me)C(鈺怱)S as the minor product. The reactivity of the pendant triple bonds in [Ni{S₂CN(CH₂C鈮H)Me}₂] was probed in the reaction with [RuH(CO)(S₂P(OEt)₂)(PPh₃)₂] to form the trimetallic example [Ni{S₂CN(Me)CH₂CH鈺怌HRu(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鈮H)Me was also used to prepare the gold nanoparticles, Au@S₂CN(CH₂C鈮H)Me. Structural studies are reported for [Ru(CH鈺怌HC₆H₄Me-4){S₂CN(CH₂CH鈺怌H₂)Me}(CO)(PPh₃)₂] and [Ru{S₂CN(CH₂C鈮H)Me}(dppm)₂]PF₆.}