Thiapentadlenyl-Iridium-Phosphine Chemistry. Synthesis of Sulfur-Containing Iridacycles via C-H Bond Activation

John R. Bleeke; Michael F. Ortwerth; Michael Y. Chiang

doi:10.1021/om00044a002

Thiapentadlenyl-Iridium-Phosphine Chemistry. Synthesis of Sulfur-Containing Iridacycles via C-H Bond Activation

John R. Bleeke, Michael F. Ortwerth, Michael Y. Chiang

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

46 Scopus citations

Abstract

Treatment of (Cl)Ir(PR₃)₃ (R = Me, Et) with potassium thiapentadienide produces ((1,2,5-η)-5-thiapentadienyl) Ir(PR₃)3 (1, R = Me; 2, R = Et). While 1 is stable indefinitely in solution, 2 undergoes intramolecular activation of thiapentadienyl C-H bonds, producing a mixture of mer-(Ir—CH═CH—CH═CH—S)(PEt₃)₃(H) (3) and mer-(Ir—C(═CH₂)—CH═CH—S)(PEt₃)₃(H) (4). Over time, all of the six-membered thiairidacycle 3 converts to the thermodynamically favored five-membered-ring compound 4.

Original language	English
Pages (from-to)	2740-2743
Number of pages	4
Journal	Organometallics
Volume	11
Issue number	8
DOIs	https://doi.org/10.1021/om00044a002
State	Published - Aug 1 1992

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title = "Thiapentadlenyl-Iridium-Phosphine Chemistry. Synthesis of Sulfur-Containing Iridacycles via C-H Bond Activation",

abstract = "Treatment of (Cl)Ir(PR3)3 (R = Me, Et) with potassium thiapentadienide produces ((1,2,5-η)-5-thiapentadienyl) Ir(PR3)3 (1, R = Me; 2, R = Et). While 1 is stable indefinitely in solution, 2 undergoes intramolecular activation of thiapentadienyl C-H bonds, producing a mixture of mer-(Ir—CH═CH—CH═CH—S)(PEt3)3(H) (3) and mer-(Ir—C(═CH2)—CH═CH—S)(PEt3)3(H) (4). Over time, all of the six-membered thiairidacycle 3 converts to the thermodynamically favored five-membered-ring compound 4.",

author = "Bleeke, \{John R.\} and Ortwerth, \{Michael F.\} and Chiang, \{Michael Y.\}",

year = "1992",

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doi = "10.1021/om00044a002",

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T1 - Thiapentadlenyl-Iridium-Phosphine Chemistry. Synthesis of Sulfur-Containing Iridacycles via C-H Bond Activation

AU - Bleeke, John R.

AU - Ortwerth, Michael F.

AU - Chiang, Michael Y.

PY - 1992/8/1

Y1 - 1992/8/1

N2 - Treatment of (Cl)Ir(PR3)3 (R = Me, Et) with potassium thiapentadienide produces ((1,2,5-η)-5-thiapentadienyl) Ir(PR3)3 (1, R = Me; 2, R = Et). While 1 is stable indefinitely in solution, 2 undergoes intramolecular activation of thiapentadienyl C-H bonds, producing a mixture of mer-(Ir—CH═CH—CH═CH—S)(PEt3)3(H) (3) and mer-(Ir—C(═CH2)—CH═CH—S)(PEt3)3(H) (4). Over time, all of the six-membered thiairidacycle 3 converts to the thermodynamically favored five-membered-ring compound 4.

AB - Treatment of (Cl)Ir(PR3)3 (R = Me, Et) with potassium thiapentadienide produces ((1,2,5-η)-5-thiapentadienyl) Ir(PR3)3 (1, R = Me; 2, R = Et). While 1 is stable indefinitely in solution, 2 undergoes intramolecular activation of thiapentadienyl C-H bonds, producing a mixture of mer-(Ir—CH═CH—CH═CH—S)(PEt3)3(H) (3) and mer-(Ir—C(═CH2)—CH═CH—S)(PEt3)3(H) (4). Over time, all of the six-membered thiairidacycle 3 converts to the thermodynamically favored five-membered-ring compound 4.

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U2 - 10.1021/om00044a002

DO - 10.1021/om00044a002

M3 - Article

AN - SCOPUS:0000323930

SN - 0276-7333

VL - 11

SP - 2740

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JO - Organometallics

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IS - 8

ER -

Thiapentadlenyl-Iridium-Phosphine Chemistry. Synthesis of Sulfur-Containing Iridacycles via C-H Bond Activation

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