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

• Published in: Inorganic chemistry 2014-11, Vol.53 (21), p.11740-11748
• Main Authors: Hurtubise, Venesia L, McArdle, James M, Naeem, Saira, Toscani, Anita, White, Andrew J. P, Long, Nicholas J, Wilton-Ely, James D. E. T
• Format: Article
• Language: English
• Subjects: Carbamates - chemistry; Crystallography, X-Ray; Ligands; Models, Molecular; Molecular Structure; Nanoparticles - chemistry; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Rhodium - chemistry; Temperature
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic502015c

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.