Combinative use of high-pressure, metal-templating and sulfur-nucleophilicity towards dithiacyclophane synthesis and its complex intermediates

Siew Huay Chong, David J. Young, T. S. Andy Hor

Research output: Contribution to journalArticleResearchpeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)349-355
Number of pages7
JournalJournal of Organometallic Chemistry
Volume691
Issue number3
DOIs
Publication statusPublished - 15 Jan 2006
Externally publishedYes

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Sulfur
Propane
propane
sulfur
Metals
Pressure
xylene
Xylene
synthesis
Ethane
ethane
metals
Byproducts
Cations
liquid phases
templates
Crystal structure
Positive ions
methylidyne
cations

Cite this

@article{3df944be342a4bbda6b0e9918be4a739,
title = "Combinative use of high-pressure, metal-templating and sulfur-nucleophilicity towards dithiacyclophane synthesis and its complex intermediates",
abstract = "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.",
keywords = "Dithiacyclophane, High-pressure, Nucleophilicity, Platinum, Sulfide, Template",
author = "Chong, {Siew Huay} and Young, {David J.} and {Andy Hor}, {T. S.}",
year = "2006",
month = "1",
day = "15",
doi = "10.1016/j.jorganchem.2005.08.055",
language = "English",
volume = "691",
pages = "349--355",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "3",

}

Combinative use of high-pressure, metal-templating and sulfur-nucleophilicity towards dithiacyclophane synthesis and its complex intermediates. / Chong, Siew Huay; Young, David J.; Andy Hor, T. S.

In: Journal of Organometallic Chemistry, Vol. 691, No. 3, 15.01.2006, p. 349-355.

Research output: Contribution to journalArticleResearchpeer-review

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

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U2 - 10.1016/j.jorganchem.2005.08.055

DO - 10.1016/j.jorganchem.2005.08.055

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EP - 355

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

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