title: Multimetallic complexes based on a diphosphine-dithiocarbamate "Janus" ligand.
abstract: The HCl salt of the aminodiphosphine ligand HN(CH2CH2PPh2)2 reacts with [M(CO)4(pip)2] (M = Mo, W; pip = piperidine) to yield [M{κ(2)-HN(CH2CH2PPh2)2}(CO)4]. The molybdenum analogue readily loses a carbonyl ligand to form [Mo{κ(3)-HN(CH2CH2PPh2)2}(CO)3], which was structurally characterized. The same ligand backbone is used to form the new bifunctional ligand, KS2CN(CH2CH2PPh2)2, which reacts with nickel and cobalt precursors to yield [Ni{S2CN(CH2CH2PPh2)2}2] and [Co{S2CN(CH2CH2PPh2)2}3]. Addition of [AuCl(tht)] (tht = tetrahydrothiophene) to [Ni{S2CN(CH2CH2PPh2)2}2] leads to formation of the pentametallic complex, [Ni{S2CN(CH2CH2PPh2AuCl)2}2]. In contrast, addition of [PdCl2(py)2] (py = pyridine) to [Ni{S2CN(CH2CH2PPh2)2}2] does not lead to a trimetallic complex but instead yields the transmetalated cyclic compound [Pd{S2CN(CH2CH2PPh2)2}]2, which was structurally characterized. The same product is obtained directly from [PdCl2(py)2] and KS2CN(CH2CH2PPh2)2. In contrast, the same reaction with [PtCl2(NCPh)2] yields the oligomer, [Pt{S2CN(CH2CH2PPh2)2}]n. Reaction of KS2CN(CH2CH2PPh2)2 with cis-[RuCl2(dppm)2] provides [Ru{S2CN(CH2CH2PPh2)2}(dppm)2](+), which reacts with [AuCl(tht)] to yield [Ru{S2CN(CH2CH2PPh2AuCl)2}(dppm)2](+). Addition of [M(CO)4(pip)2] (M = Mo, W) to the same precursor leads to formation of the bimetallic compounds [(dppm)2Ru{S2CN(CH2CH2PPh2)2}M(CO)4](+), while treatment with [ReCl(CO)5] yields [(dppm)2Ru{S2CN(CH2CH2PPh2)2}ReCl(CO)3](+). Reaction of KS2CN(CH2CH2PPh2)2 with [Os(CH═CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) provides [Os(CH═CHC6H4Me-4){S2CN(CH2CH2PPh2)2}(CO)(PPh3)2], but reaction with the analogous ruthenium precursor fails to yield a clean product.
authors.affiliation: †Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Rebecca
authors.initials: R
authors.lastname: Sherwood
authors.affiliation: †Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.|‡Departament de Química Inorgànica, Universitat de Barcelona, Martí Franquès 1-11, 08028, Barcelona, Spain.
authors.forename: Ferran
authors.initials: F
authors.lastname: Gonzàlez de Rivera
authors.affiliation: †Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Jane Hui
authors.initials: JH
authors.lastname: Wan
authors.affiliation: §Hainan Provincial Key Laboratory of Fine Chemicals, Hainan University, Haikou, Hainan 570228, China.
authors.forename: Qi
authors.initials: Q
authors.lastname: Zhang
authors.affiliation: †Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.affiliation: ‡Departament de Química Inorgànica, Universitat de Barcelona, Martí Franquès 1-11, 08028, Barcelona, Spain.
authors.forename: Oriol
authors.initials: O
authors.lastname: Rossell
authors.affiliation: ∥Department of Chemistry, King's College London, Britannia House, 7 Trinity Street, London SE1 1DB, U.K.
authors.forename: Graeme
authors.initials: G
authors.lastname: Hogarth
authors.affiliation: †Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, U.K.
authors.forename: James D E T
authors.initials: JD
authors.lastname: Wilton-Ely