Synthesis and Reactivity of [Ir(η2-E2R)(Ph2PCH2CH2PPh2)2]2+ (E = S, Se; R = H, CH3)

John E. Hoots; Thomas B. Rauchfuss

doi:10.1021/ic00162a009

Synthesis and Reactivity of [Ir(η²-E₂R)(Ph₂PCH₂CH₂PPh₂)₂]²⁺ (E = S, Se; R = H, CH₃)

John E. Hoots, Thomas B. Rauchfuss

Chemistry

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

Abstract

The stereochemistry and reactivity of [Ir(E₂R)(dppe)₂]²⁺ (dppe = Ph²P(CH₂)₂PPh₂; E = S, Se; R = H, CH₃) have been examined. In solution, [Ir(E₂CH₃)(dppe)₂]²⁺ exists as a mixture of two diastereomers in the ratio of 20:1 (E = S) and 6:1 (E = Se). Protonation of [Ir(E₂)(dppe)₂]⁺ with strong acids gave [Ir(E₂H)(dppe)₂]²⁺ complexes, which are spectroscopically and stereochemically similar to the η²-E₂CH₃ derivatives. In contrast to [Ir(S₂)(dppe)₂]⁺, the [Ir(S₂CH₃)(dppe)₂]²⁺ (1) complex can act as both a potent sulfur atom and CH₃S⁺ transfer reagent. The nature of the S-transfer reaction depends on the substrate (X) used and the stability of the corresponding S-X and [X-SCH₃]⁺ products. 1 reacts rapidly with PPh₃ (2 equiv) to give [Ir(dppe)₂]⁺, Ph₃PS, and [Ph₃PSCH₃]⁺. With CH₃NC (2 equiv) and 1, sulfur atom transfer occurs, and cis-[Ir(SCH₃)(CH₃NC)(dppe)₂]²⁺ and CH₃NCS are produced. Reaction of CN^- with 1 gave cis-[Ir(SCH₃)(SCN)(dppe)₂]⁺. Oxidative addition of CH₃SH and CH₃SCl to [Ir(dppe)₂]⁺ gave [Ir(SCH₃)H(dppe)₂]⁺ and [Ir(SCH₃)Cl(dppe)₂]⁺, respectively. ¹H NMR species confirmed the utility of the high-field ortho phenyl, the S₂CH₃, and the SCH₃ resonances in structure elucidation. Also described is the applicability of gel-permeation chromatography and field-desorption mass spectrometry for the purification and characterization of these ionic, high molecular weight complexes.

Original language	English (US)
Pages (from-to)	2806-2812
Number of pages	7
Journal	Inorganic Chemistry
Volume	22
Issue number	20
DOIs	https://doi.org/10.1021/ic00162a009
State	Published - Sep 1983

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{854c498a06c941759f96c429d992bc45,

title = "Synthesis and Reactivity of [Ir(η2-E2R)(Ph2PCH2CH2PPh2)2]2+ (E = S, Se; R = H, CH3)",

abstract = "The stereochemistry and reactivity of [Ir(E2R)(dppe)2]2+ (dppe = Ph2P(CH2)2PPh2; E = S, Se; R = H, CH3) have been examined. In solution, [Ir(E2CH3)(dppe)2]2+ exists as a mixture of two diastereomers in the ratio of 20:1 (E = S) and 6:1 (E = Se). Protonation of [Ir(E2)(dppe)2]+ with strong acids gave [Ir(E2H)(dppe)2]2+ complexes, which are spectroscopically and stereochemically similar to the η2-E2CH3 derivatives. In contrast to [Ir(S2)(dppe)2]+, the [Ir(S2CH3)(dppe)2]2+ (1) complex can act as both a potent sulfur atom and CH3S+ transfer reagent. The nature of the S-transfer reaction depends on the substrate (X) used and the stability of the corresponding S-X and [X-SCH3]+ products. 1 reacts rapidly with PPh3 (2 equiv) to give [Ir(dppe)2]+, Ph3PS, and [Ph3PSCH3]+. With CH3NC (2 equiv) and 1, sulfur atom transfer occurs, and cis-[Ir(SCH3)(CH3NC)(dppe)2]2+ and CH3NCS are produced. Reaction of CN- with 1 gave cis-[Ir(SCH3)(SCN)(dppe)2]+. Oxidative addition of CH3SH and CH3SCl to [Ir(dppe)2]+ gave [Ir(SCH3)H(dppe)2]+ and [Ir(SCH3)Cl(dppe)2]+, respectively. 1H NMR species confirmed the utility of the high-field ortho phenyl, the S2CH3, and the SCH3 resonances in structure elucidation. Also described is the applicability of gel-permeation chromatography and field-desorption mass spectrometry for the purification and characterization of these ionic, high molecular weight complexes.",

author = "Hoots, {John E.} and Rauchfuss, {Thomas B.}",

year = "1983",

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N2 - The stereochemistry and reactivity of [Ir(E2R)(dppe)2]2+ (dppe = Ph2P(CH2)2PPh2; E = S, Se; R = H, CH3) have been examined. In solution, [Ir(E2CH3)(dppe)2]2+ exists as a mixture of two diastereomers in the ratio of 20:1 (E = S) and 6:1 (E = Se). Protonation of [Ir(E2)(dppe)2]+ with strong acids gave [Ir(E2H)(dppe)2]2+ complexes, which are spectroscopically and stereochemically similar to the η2-E2CH3 derivatives. In contrast to [Ir(S2)(dppe)2]+, the [Ir(S2CH3)(dppe)2]2+ (1) complex can act as both a potent sulfur atom and CH3S+ transfer reagent. The nature of the S-transfer reaction depends on the substrate (X) used and the stability of the corresponding S-X and [X-SCH3]+ products. 1 reacts rapidly with PPh3 (2 equiv) to give [Ir(dppe)2]+, Ph3PS, and [Ph3PSCH3]+. With CH3NC (2 equiv) and 1, sulfur atom transfer occurs, and cis-[Ir(SCH3)(CH3NC)(dppe)2]2+ and CH3NCS are produced. Reaction of CN- with 1 gave cis-[Ir(SCH3)(SCN)(dppe)2]+. Oxidative addition of CH3SH and CH3SCl to [Ir(dppe)2]+ gave [Ir(SCH3)H(dppe)2]+ and [Ir(SCH3)Cl(dppe)2]+, respectively. 1H NMR species confirmed the utility of the high-field ortho phenyl, the S2CH3, and the SCH3 resonances in structure elucidation. Also described is the applicability of gel-permeation chromatography and field-desorption mass spectrometry for the purification and characterization of these ionic, high molecular weight complexes.

AB - The stereochemistry and reactivity of [Ir(E2R)(dppe)2]2+ (dppe = Ph2P(CH2)2PPh2; E = S, Se; R = H, CH3) have been examined. In solution, [Ir(E2CH3)(dppe)2]2+ exists as a mixture of two diastereomers in the ratio of 20:1 (E = S) and 6:1 (E = Se). Protonation of [Ir(E2)(dppe)2]+ with strong acids gave [Ir(E2H)(dppe)2]2+ complexes, which are spectroscopically and stereochemically similar to the η2-E2CH3 derivatives. In contrast to [Ir(S2)(dppe)2]+, the [Ir(S2CH3)(dppe)2]2+ (1) complex can act as both a potent sulfur atom and CH3S+ transfer reagent. The nature of the S-transfer reaction depends on the substrate (X) used and the stability of the corresponding S-X and [X-SCH3]+ products. 1 reacts rapidly with PPh3 (2 equiv) to give [Ir(dppe)2]+, Ph3PS, and [Ph3PSCH3]+. With CH3NC (2 equiv) and 1, sulfur atom transfer occurs, and cis-[Ir(SCH3)(CH3NC)(dppe)2]2+ and CH3NCS are produced. Reaction of CN- with 1 gave cis-[Ir(SCH3)(SCN)(dppe)2]+. Oxidative addition of CH3SH and CH3SCl to [Ir(dppe)2]+ gave [Ir(SCH3)H(dppe)2]+ and [Ir(SCH3)Cl(dppe)2]+, respectively. 1H NMR species confirmed the utility of the high-field ortho phenyl, the S2CH3, and the SCH3 resonances in structure elucidation. Also described is the applicability of gel-permeation chromatography and field-desorption mass spectrometry for the purification and characterization of these ionic, high molecular weight complexes.

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