Nitrogen atom insertion into IR - S and C - S bonds initiated by photolysis of iridium(III) - azido-dithiocarbamato complexes

Takayoshi Suzuki, Antonio G. DiPasquale, James M. Mayer

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Photolysis of acetonitrile solutions of Cp*Ir(R2dtc)(N3) [Cp* = η5-C5Me5, R2dtc = S2CNR2; R = Me (1) or Et (1′)] at temperatures below 0 °C afford five-coordinate complexes Cp*Ir{NSC(NR2)S} (2 or 2′), where a nitrogen atom has been inserted into one of the Ir-S bonds. In solution, complex 2 thermally convert to the azaethene-1,2-dithiolate complex, Cp*Ir[SN=C(NMe2)S] (3), which could be crystallized as the corresponding dimer, {Cp*Ir[μ-SN=C(NMe2)S-κ3S:S,S′]}2 (4). As a result, a nitrogen atom that originated in the azide ligand is transferred into a C-S bond of the dithiocarbamate.

Original languageEnglish
Pages (from-to)10514-10515
Number of pages2
JournalJournal of the American Chemical Society
Volume125
Issue number35
DOIs
Publication statusPublished - Sep 3 2003
Externally publishedYes

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Iridium
Photolysis
Nitrogen
Atoms
Azides
Acetonitrile
Dimers
Ligands
Temperature
protein-bound SN-C polysaccharide
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Nitrogen atom insertion into IR - S and C - S bonds initiated by photolysis of iridium(III) - azido-dithiocarbamato complexes. / Suzuki, Takayoshi; DiPasquale, Antonio G.; Mayer, James M.

In: Journal of the American Chemical Society, Vol. 125, No. 35, 03.09.2003, p. 10514-10515.

Research output: Contribution to journalArticle

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abstract = "Photolysis of acetonitrile solutions of Cp*Ir(R2dtc)(N3) [Cp* = η5-C5Me5, R2dtc = S2CNR2; R = Me (1) or Et (1′)] at temperatures below 0 °C afford five-coordinate complexes Cp*Ir{NSC(NR2)S} (2 or 2′), where a nitrogen atom has been inserted into one of the Ir-S bonds. In solution, complex 2 thermally convert to the azaethene-1,2-dithiolate complex, Cp*Ir[SN=C(NMe2)S] (3), which could be crystallized as the corresponding dimer, {Cp*Ir[μ-SN=C(NMe2)S-κ3S:S,S′]}2 (4). As a result, a nitrogen atom that originated in the azide ligand is transferred into a C-S bond of the dithiocarbamate.",
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N2 - Photolysis of acetonitrile solutions of Cp*Ir(R2dtc)(N3) [Cp* = η5-C5Me5, R2dtc = S2CNR2; R = Me (1) or Et (1′)] at temperatures below 0 °C afford five-coordinate complexes Cp*Ir{NSC(NR2)S} (2 or 2′), where a nitrogen atom has been inserted into one of the Ir-S bonds. In solution, complex 2 thermally convert to the azaethene-1,2-dithiolate complex, Cp*Ir[SN=C(NMe2)S] (3), which could be crystallized as the corresponding dimer, {Cp*Ir[μ-SN=C(NMe2)S-κ3S:S,S′]}2 (4). As a result, a nitrogen atom that originated in the azide ligand is transferred into a C-S bond of the dithiocarbamate.

AB - Photolysis of acetonitrile solutions of Cp*Ir(R2dtc)(N3) [Cp* = η5-C5Me5, R2dtc = S2CNR2; R = Me (1) or Et (1′)] at temperatures below 0 °C afford five-coordinate complexes Cp*Ir{NSC(NR2)S} (2 or 2′), where a nitrogen atom has been inserted into one of the Ir-S bonds. In solution, complex 2 thermally convert to the azaethene-1,2-dithiolate complex, Cp*Ir[SN=C(NMe2)S] (3), which could be crystallized as the corresponding dimer, {Cp*Ir[μ-SN=C(NMe2)S-κ3S:S,S′]}2 (4). As a result, a nitrogen atom that originated in the azide ligand is transferred into a C-S bond of the dithiocarbamate.

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