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Formation of Methane versus Benzene in the Reactions of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with [CH 3 PPh 3 ]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [1];  [1];  [2];  [1]
  1. Department of Chemistry University of Missouri Columbia MO 65211 USA
  2. Universite de Toulouse and CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO 135 Avenue de Rangueil 31077 Toulouse France
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Abstract

The reaction of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with the phosphonium salts [CH 3 PPh 3 ]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C 5 Me 5 ) 2 Th[CHPPh 3 ]X, rare terminal phosphorano‐stabilized carbenes with thorium. These complexes feature the shortest thorium–carbon bonds (≈2.30 Å) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C 5 Me 5 ) 2 Th[κ 2 ‐(C,C′)‐(CH 2 )(CH 2 )PPh 2 ]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH 3 PPh 3 ]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene.

Sponsoring Organization:
USDOE
Grant/Contract Number:
NONE; SC0014174
OSTI ID:
1379993
Alternate ID(s):
OSTI ID: 1537447
OSTI ID: 22642872
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 42 Vol. 56; ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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