Ring expansion of a platinacyclopropane to a platinacyclopentane by double insertion of isocyanides into Pt-C bonds

Kazuhiro Tsuchiya, Hideo Kondo, Hideo Nagashima

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

A platinum isocyanide complex bearing a η2-TCNE ligand, (η2-TCNE)Pt(η-CNC6H3-2,6-Me 2)2 (1), was synthesized, and its crystallographic study revealed the coordination mode of the η2-TCNE ligand to be a typical metallacyclopropane extreme, in which back-donation from metal to TCNE contributes primarily to the stabilization of 1. Treatment of 1 with 2 equiv of CNC6H3-2,6-Me2 resulted in ring expansion of the platinacyclopropane by insertion of CNC6H3-2,6-Me 2 into each Pt-C bond of the metallacycle, leading to formation of a new complex having a platinacyclopentane structure, (TCNE)Pt(η-CNC 6H3-2,6-Me2)4 (4). Although the molecular structures of palladium and nickel homologues of 1 were close to the corresponding metallacyclopropane, no metallacyclopentane complex was obtained under similar conditions. Studies on variable-temperature NMR spectroscopy and spin-saturation transfer measurement of 4 showed exchange of the imidoyl CNC6H3-2,6-Me2 group and the coordinated CNC6H3-2,6-Me2 ligand in solution, suggesting the ring expansion to be reversible.

Original languageEnglish
Pages (from-to)1044-1051
Number of pages8
JournalOrganometallics
Volume26
Issue number4
DOIs
Publication statusPublished - Feb 12 2007

Fingerprint

Cyanides
insertion
Ligands
ligands
expansion
rings
Bearings (structural)
Palladium
Platinum
Nickel
Molecular structure
Nuclear magnetic resonance spectroscopy
palladium
platinum
molecular structure
Stabilization
stabilization
Metals
nickel
saturation

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Ring expansion of a platinacyclopropane to a platinacyclopentane by double insertion of isocyanides into Pt-C bonds. / Tsuchiya, Kazuhiro; Kondo, Hideo; Nagashima, Hideo.

In: Organometallics, Vol. 26, No. 4, 12.02.2007, p. 1044-1051.

Research output: Contribution to journalArticle

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AB - A platinum isocyanide complex bearing a η2-TCNE ligand, (η2-TCNE)Pt(η-CNC6H3-2,6-Me 2)2 (1), was synthesized, and its crystallographic study revealed the coordination mode of the η2-TCNE ligand to be a typical metallacyclopropane extreme, in which back-donation from metal to TCNE contributes primarily to the stabilization of 1. Treatment of 1 with 2 equiv of CNC6H3-2,6-Me2 resulted in ring expansion of the platinacyclopropane by insertion of CNC6H3-2,6-Me 2 into each Pt-C bond of the metallacycle, leading to formation of a new complex having a platinacyclopentane structure, (TCNE)Pt(η-CNC 6H3-2,6-Me2)4 (4). Although the molecular structures of palladium and nickel homologues of 1 were close to the corresponding metallacyclopropane, no metallacyclopentane complex was obtained under similar conditions. Studies on variable-temperature NMR spectroscopy and spin-saturation transfer measurement of 4 showed exchange of the imidoyl CNC6H3-2,6-Me2 group and the coordinated CNC6H3-2,6-Me2 ligand in solution, suggesting the ring expansion to be reversible.

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