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η6-Coordinated ruthenabenzenes from three-component assembly on a diruthenium μ-allenyl scaffold.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 6/7/2022, Vol. 51 Issue 21, p8390-8400, 11p
- Publication Year :
- 2022
-
Abstract
- The room temperature reactions with internal alkynes, RC≡CR, of the μ-allenyl acetonitrile complex [Ru<subscript>2</subscript>Cp<subscript>2</subscript>(CO)<subscript>2</subscript>(NCMe){μ–η<superscript>1</superscript>:η<superscript>2</superscript>-C<superscript>1</superscript>H=C<superscript>2</superscript>=C<superscript>3</superscript>Me<subscript>2</subscript>}]BF<subscript>4</subscript> (1-NCMe), freshly prepared from the tricarbonyl precursor [Ru<subscript>2</subscript>Cp<subscript>2</subscript>(CO)<subscript>3</subscript>{μ–η<superscript>1</superscript>:η<superscript>2</superscript>-C<superscript>1</superscript>H=C<superscript>2</superscript>=C<superscript>3</superscript>Me<subscript>2</subscript>}]BF<subscript>4</subscript>, 1, proceeded with alkyne insertion into ruthenium-allenyl bond and allenyl-CO coupling, affording compounds [Ru<subscript>2</subscript>Cp<subscript>2</subscript>(CO)<subscript>2</subscript>{μ–η<superscript>2</superscript>:η<superscript>5</superscript>-C(R)C(R)C<superscript>1</superscript>HC<superscript>2</superscript>(C<superscript>3</superscript>Me=CH<subscript>2</subscript>)C(OH)}]BF<subscript>4</subscript> (R = Ph, 2; R = CO<subscript>2</subscript>Me, 3; R = CO<subscript>2</subscript>Et, 4) in 83–94% yields. Deprotonation of 2–4 by triethylamine gave [Ru<subscript>2</subscript>Cp<subscript>2</subscript>(CO)<subscript>2</subscript>{μ–η<superscript>2</superscript>:η<superscript>5</superscript>-C(R)C(R)CHC(CMe=CH<subscript>2</subscript>)C(O)}] (R = Ph, 5; R = CO<subscript>2</subscript>Me, 6; R = CO<subscript>2</subscript>Et, 7) in 75–88% yields, and 2–4 could be recovered upon HBF<subscript>4</subscript>·Et<subscript>2</subscript>O addition to 5–7. All the products, 2–7, were fully characterized by elemental analysis, IR and multinuclear NMR spectroscopy. The structure of 2 was ascertained by single crystal X-ray diffraction and investigated by DFT calculations, revealing a six-membered ruthenacycle with Shannon aromaticity index in line with related compounds. The formation of ruthenium-coordinated ruthenabenzenes from a preexistent diruthenium scaffold is a versatile but underdeveloped approach exploiting cooperative effects typical of a dimetallic core. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 51
- Issue :
- 21
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 157177788
- Full Text :
- https://doi.org/10.1039/d2dt01071b