TY - JOUR
T1 - Combinative use of high-pressure, metal-templating and sulfur-nucleophilicity towards dithiacyclophane synthesis and its complex intermediates
AU - Chong, Siew Huay
AU - Young, David J.
AU - Andy Hor, T. S.
PY - 2006/1/15
Y1 - 2006/1/15
N2 - Combined use of elevated pressure in the liquid phase (15 kbar), a metal template and the sulfur nucleophilicity of [Pt2(μ-S) 2(P-P)2] (P-P = diphosphine or 2 • monophosphine) facilitates the one-pot synthesis of 3,8-dibenzo-1,6-dithiacyclodecane. Under r.t.p., nucleophilic addition of [Pt2(μ-S)2(P-P) 2] [P-P = 2 • PPh3; Ph2P(CH 2)nPPh2, n = 2, 1,2-bis(diphenylphosphino) ethane (dppe), 3, 1,3-bis(diphenylphosphino)propane (dppp)] with α-α′-dichloro-o-xylene would terminate as a dithiolato bridged cation viz. [Pt2(μ-SCH2C6H 4CH2S)(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(μ-SCH 2C6H4CH2S)(P-P)2] 2+ for PPh3 and dppp have been isolated as PF6- 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.
AB - Combined use of elevated pressure in the liquid phase (15 kbar), a metal template and the sulfur nucleophilicity of [Pt2(μ-S) 2(P-P)2] (P-P = diphosphine or 2 • monophosphine) facilitates the one-pot synthesis of 3,8-dibenzo-1,6-dithiacyclodecane. Under r.t.p., nucleophilic addition of [Pt2(μ-S)2(P-P) 2] [P-P = 2 • PPh3; Ph2P(CH 2)nPPh2, n = 2, 1,2-bis(diphenylphosphino) ethane (dppe), 3, 1,3-bis(diphenylphosphino)propane (dppp)] with α-α′-dichloro-o-xylene would terminate as a dithiolato bridged cation viz. [Pt2(μ-SCH2C6H 4CH2S)(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(μ-SCH 2C6H4CH2S)(P-P)2] 2+ for PPh3 and dppp have been isolated as PF6- 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.
KW - Dithiacyclophane
KW - High-pressure
KW - Nucleophilicity
KW - Platinum
KW - Sulfide
KW - Template
UR - http://www.scopus.com/inward/record.url?scp=29344447486&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2005.08.055
DO - 10.1016/j.jorganchem.2005.08.055
M3 - Article
AN - SCOPUS:29344447486
VL - 691
SP - 349
EP - 355
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 3
ER -