Synthesis, Structure, and CO 2 Reactivity of a Two-Coordinate (Carbene)copper(I) Methyl Complex

Organometallics

Volumn 23, Issue 6, 2004, Pages 1191-1193

  Mankad, Neal P ^a   Gray, Thomas G ^a   Laitar, David S ^a   Sadighi, Joseph P ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BINUCLEAR REACTION; METHYLATION;

BENZENE; CARBOXYLATION; CATALYSIS; CHEMICAL BONDS; COPPER COMPOUNDS; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS (CHEMICAL); TRANSITION METALS;

ORGANOMETALLICS;

EID: 1842429742     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om034368r     Document Type: Article

References (51)

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28. For complete synthetic, computational, spectroscopic, and crystallographic details, see the Supporting Information.
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30. 2) = 0.1651, and GOF = 1.058 based on I > 2σ(I).
31. (a) Thiele, K.-H.; Koehler, J. J. Organomet. Chem. 1968, 12, 225-229. See also ref 2c.
32. Copper(I) acetate (1.06 g, 2.74 mmol) and IPr (0.336 g, 2.74 mmol) were stirred in toluene (25 mL) for 11 h. The resulting solution was filtered through Celite and then concentrated. The crude product was triturated with hexanes (3 × 20 mL) and then dried in vacuo, affording 2 as a white powder; yield 0.777 g (56%).
33. Taqui Khan, M. M.; Paul, P.; Venkatasubramanian, K.; Purohit, S. Inorg. Chim. Acta 1991, 183, 229-237. See also ref 15c.
34. 2) = 0.1408, and GOF = 1.029 based on I > 2σ(I).
35. -1 region, which mask the peaks calculated for the symmetric vibration in both model complexes A and B. We thank a reviewer for raising this point.
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42. All calculated vibrational frequencies for A and B are real, indicating that both forms represent stable minima.
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45. 2-bound form but longer than the intermolecular approaches in the actual structure. We thank a reviewer for raising this point.
46. Dimethylaluminum ethoxide, generated in situ from trimethylaluminum (2.0 mmol) and ethanol (0.117 mL, 2.0 mmol) in toluene/diethyl ether solution (1:1,2 mL), was transferred by cannula to a -45°C suspension of 2 (0.396 g, 0.776 mmol) in diethyl ether (3 mL). The reaction mixture was warmed gradually to room temperature with stirring over 4 h and then concentrated to afford a crude yellow solid. This solid was taken up in hexanes (5 mL), and the precipitate was collected by filtration and washed repeatedly with hexanes. Yield: 0.256 g (71%).
47. 2) = 0.1758, and GOF = 1.158 based on I > 2σ(I).
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50. A solution of 3 (0.0683 g, 0.147 mmol) in benzene (4 mL) was frozen at -78°C in the dark. The reaction vessel was evacuated and back-filled with carbon dioxide (ca. 1 atm). The reaction mixture was then thawed, warmed to room temperature, and stirred for 18 h. Concentration in vacuo afforded a tan powder; yield 72.1 mg (96%).
51. 2) and judged to be 50% complete after 65 min and 95% complete after 2.5 h.