Combinative use of high-pressure, metal-templating and sulfur-nucleophilicity towards dithiacyclophane synthesis and its complex intermediates
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Combined use of elevated pressure in the liquid phase (15 kbar), a metal template and the sulfur nucleophilicity of [Pt2(孓)2(P-P)2] (P-P = diphosphine or 2 砭onophosphine) facilitates the one-pot synthesis of 3,8-dibenzo-1,6-dithiacyclodecane. Under r.t.p., nucleophilic addition of [Pt2(孓)2(P-P)2] [P-P = 2 砐Ph3; Ph2P(CH2)nPPh2, n = 2, 1,2-bis(diphenylphosphino)ethane (dppe), 3, 1,3-bis(diphenylphosphino)propane (dppp)] with a-a'-dichloro-o-xylene would terminate as a dithiolato bridged cation viz. [Pt2(孓CH2C6H4CH2S)(P-P)2]2+. Under high pressure (15 kbar) at r.t., these stoichiometric reactions progress via a "catalytic-like" pathway to yield 3,8-dibenzo-1,6-dithiacyclodecane (up to 35%), and a series of mechanistically relevant intermediates and byproducts. The dithiolated intermediates [Pt2(孓CH2C6H4CH2S)(P-P)2]2+ for PPh3 and dppp have been isolated as View the MathML source complexes and their crystal structure determined. The formation of 3,8-dibenzo-1,6-dithiacyclodecane demonstrates a convenient synthetic strategy over the multi-step synthesis of this macrocyclic dithioether.
Journal of Organometallic Chemistry
Copyright 2006 Elsevier. Please refer to the journal's website for access to the definitive, published version.