title: Multimetallic complexes and functionalized nanoparticles based on unsymmetrical dithiocarbamate ligands with allyl and propargyl functionality.
abstract: 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.
authors.affiliation: Department of Chemistry, Imperial College London , South Kensington Campus, London SW7 2AZ, United Kingdom.
authors.forename: Venesia L
authors.initials: VL
authors.lastname: Hurtubise
authors.forename: James M
authors.initials: JM
authors.lastname: McArdle
authors.forename: Saira
authors.initials: S
authors.lastname: Naeem
authors.forename: Anita
authors.initials: A
authors.lastname: Toscani
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Long
authors.forename: James D E T
authors.initials: JD
authors.lastname: Wilton-Ely
mesh_terms: D002219:Carbamates / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013696:Temperature
chemical_list: D002219:Carbamates; D008024:Ligands; D009942:Organometallic Compounds; D012238:Rhodium