Highly Reduced Carbene Complexes: Formation of an Alkoxymalonate by Coupling of Carbon Dioxide with the Nucleophilic Carbene in (Cr(CO4)=C(OMe)PH)2-

Abstract

Reduction of a mixture of cis and trans (Cr(C0)4(PBu3)(C(OMe)Ph)) with 2.0 equiv. of potassium naphthalenide leads to formation of a highly reduced complex with carbonyl absorptions at 1859(s) and 1737(s) cm-1, consistent with formation of the dianionic carbene complex (Cr(CO)4(C(OMe)Ph)) (2-)(1(2-). A crystalline salt of 1(2-) can be obtained by 18-crown-6 complexation of the K+ counterion of samples prepared by reduction of TRANS(Cr(CO)4(PCy3)-(C(OMe)Ph)). The proposed formulation is supported by an unprecedented bis-carboxylation of the carbene ligand in 12- to give the unusual methoxy-malonate K2(Ph(MeO)C(CO2))2) (K25, 82%), characterized by H+/CH2N2 esterification to give Ph(MeO)C(CO2Me)2 in 85% yield. The malonate K25 can be prepared directly from readily available (Cr(CO)5(C(OMe)Ph)) (2) in a single pot in 53% overall yield. (kt)

Open PDF

Document Details

Document Type
Technical Report
Publication Date
Nov 17, 1989
Accession Number
ADA215132

Entities

People

  • John A Cooper
  • Samkeun Lee

Organizations

  • University of Pittsburgh

Tags

Communities of Interest

  • Weapons Technologies

DTIC Thesaurus Topics

  • Absorption
  • Abstracts
  • Alkali Metals
  • Carbon Dioxide
  • Chemical Compounds
  • Chemistry
  • Classification
  • Couplings
  • Electron Transfer
  • Elements
  • Metals
  • Military Research
  • Organic Chemistry
  • Potassium
  • Security
  • Transition Metals
  • Transitions

Fields of Study

  • Chemistry

Readers

  • Mathematics or Statistics
  • Organic Chemistry