Facile Metal‐Mediated Synthesis of Macrocyclic Diselenoethers

Abstract

Nucleophilic attack of [Pt2(μ‐Se)2(PPh3)4] on dihaloalkanes gives stable diselenolato complexes, which release macrocyclic diselenoethers upon treatment with dihaloalkanes. The overhead‐bridged diplatinum intermediates have been isolated and structurally characterized by single‐crystal X‐ray crystallography. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2003)

Extending The Reaction Landscape of the {Pt(μ‐S)2Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

“…[7] These reactions led to the corresponding monoalkylated cation [L 2 Pt(µ-S)(µ-SR) 2 ] with 100-fold excess of 1,2-dichloroethane. [65] Similar double alkylations have been achieved in complexes containing the {Pt(µ-Se) 2 Pt} [66,67] or {Ni(µ-S) 2 Ni} [18] core. A particular case of the previous reaction involving organic halides is the surprising progression of [L 2 Pt(µ-S) 2 PtL 2 ] compounds when they are dissolved in chlorinated solvents, mainly CH 2 Cl 2 .…”

Mixed-chalcogenide diplatinum complexes; an investigation of ligand exchange processes using ESI mass spectrometry

“…[4,5] The related selenide complex [Pt2(µ-Se)2(PPh3)4] 2 has been less-intensively studied, [6] but has distinctive reactivity differences compared to its sulfide counterpart. [7,8,9] The chemistry of these complexes, which has been reviewed on a number of occasions, [10,11,12,13] is dominated by their alkylation and arylation reactions with suitable electrophiles, and their reactivity as metalloligands, forming sulfide-bridged multi-metallic complexes. Despite their extensive chemistry, new pathways of reactivity continue to be developed, such as in the reactivity towards a chloropyridinium salt and NH3, resulting in the formation of the novel binuclear platinum µ-amido complex [Pt2(µ-S)(µ-NH2)(PPh3) 4] + .…”

Hydroxo and Oxo Complexes of Platinum(II) Stabilized by Phosphanes: Synthesis and Characterization − X‐ray Structures of cis‐[L2Pt(μ‐OH)]2(NO3)2 (L = PMe2Ph, PMePh2) and [{cis‐(PMe2Ph)2Pt}3(μ‐O)2]Cl2

“…Under the same experimental conditions, the structurally analogous hydroxo complex, stabilized by the less basic and more hindered PMePh 2 2 ] 2ϩ species in which the relative quantity of the two compounds is strongly dependent on the amount of added chloride. A large excess of Cl Ϫ ions leads to the formation of cis-[L 2 PtCl 2 ] as the main product, whereas relatively good yields of the oxo complex are formed when the molar ratio n (Cl Ϫ ) /n (hydroxo complex) approaches the value of 2:1. This finding contrasts the observations reported by Bushnell for the strictly related hydroxo complex stabilized by PEt 3 .…”

“…[1] They were obtained by deprotonation of the corresponding hydroxo bridged complexes [L 2 Pt(µ-OH)] 2 2ϩ with strong bases such as LiN(SiMe 3 ) 2 . A common feature of the bridging oxo ligands, and their chalcogenide analogues, [2] is the ability to bind ions such as Li ϩ , Ag ϩ , Cu ϩ , and other metal centers, thus affording stable and well-characterized heteropolymetallic complexes.…”

“…[1] They were obtained by deprotonation of the corresponding hydroxo bridged complexes [L 2 Pt(µ-OH)] 2 2ϩ with strong bases such as LiN(SiMe 3 ) 2 . A common feature of the bridging oxo ligands, and their chalcogenide analogues, [2] is the ability to bind ions such as Li ϩ , Ag ϩ , Cu ϩ , and other metal centers, thus affording stable and well-characterized heteropolymetallic complexes. An exception is represented by the adduct [cis-L 2 Pt(µ-O)] 2 ·2LiBF 4 (L ϭ PMe 2 Ph), which decomposes in THF to give [{cis-L 2 Pt} 3 (µ-O) 2 ](BF 4 ) 2 (Scheme 1), the trinuclear species in which each oxygen atom is symmetrically coordinated to three [L 2 Pt] 2ϩ units.…”