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Structure and Reactivity of [Ru-Al] and [Ru-Sn] Heterobimetallic PPh 3 -Based Complexes.
- Source :
-
Organometallics [Organometallics] 2022 Oct 10; Vol. 41 (19), pp. 2716-2730. Date of Electronic Publication: 2022 Sep 21. - Publication Year :
- 2022
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Abstract
- Treatment of [Ru(PPh <subscript>3</subscript> )(C <subscript>6</subscript> H <subscript>4</subscript> PPh <subscript>2</subscript> ) <subscript>2</subscript> H][Li(THF) <subscript>2</subscript> ] with AlMe <subscript>2</subscript> Cl and SnMe <subscript>3</subscript> Cl leads to elimination of LiCl and CH <subscript>4</subscript> and formation of the heterobimetallic complexes [Ru(C <subscript>6</subscript> H <subscript>4</subscript> PPh <subscript>2</subscript> ) <subscript>2</subscript> {PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> AlMe(THF)}H] 5 and [Ru(PPh <subscript>3</subscript> )(C <subscript>6</subscript> H <subscript>4</subscript> PPh <subscript>2</subscript> )(PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> SnMe <subscript>2</subscript> )] 6 , respectively. The pathways to 5 and 6 have been probed by variable temperature NMR studies, together with input from DFT calculations. Complete reaction of H <subscript>2</subscript> occurs with 5 at 60 °C and with 6 at room temperature to yield the spectroscopically characterized trihydride complexes [Ru(PPh <subscript>2</subscript> ) <subscript>2</subscript> {PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> AlMe}H <subscript>3</subscript> ] 7 and [Ru(PPh <subscript>2</subscript> ) <subscript>2</subscript> {PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> SnMe <subscript>2</subscript> }H <subscript>3</subscript> ] 8 . In the presence of CO, 6 forms the acylated phosphine complex, [Ru(CO) <subscript>2</subscript> (C(O)C <subscript>6</subscript> H <subscript>4</subscript> PPh <subscript>2</subscript> )(PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> SnMe <subscript>2</subscript> )] 9 , through a series of intermediates that were identified by NMR spectroscopy in conjunction with <superscript>13</superscript> CO labeling. Complex 6 undergoes addition and substitution reactions with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (IMe <subscript>4</subscript> ) to give [Ru(IMe <subscript>4</subscript> ) <subscript>2</subscript> (PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> )(PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> SnMe <subscript>2</subscript> )] 10 , which converted via rare N-Me group C-H activation to [Ru(IMe <subscript>4</subscript> )(PPh <subscript>3</subscript> )(IMe <subscript>4</subscript> )'(PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> SnMe <subscript>2</subscript> )] 11 upon heating at 60 °C and to a mixture of [Ru(IMe <subscript>4</subscript> ) <subscript>2</subscript> (IMe <subscript>4</subscript> )'(PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> SnMe <subscript>2</subscript> )] 12 and [Ru(PPh <subscript>3</subscript> )(PPh <subscript>2</subscript> C <subscript>6</subscript> H <subscript>4</subscript> )(IMe <subscript>4</subscript> -SnMe <subscript>2</subscript> )'] 13 at 120 °C.<br />Competing Interests: The authors declare no competing financial interest.<br /> (© 2022 The Authors. Published by American Chemical Society.)
Details
- Language :
- English
- ISSN :
- 0276-7333
- Volume :
- 41
- Issue :
- 19
- Database :
- MEDLINE
- Journal :
- Organometallics
- Publication Type :
- Academic Journal
- Accession number :
- 36249448
- Full Text :
- https://doi.org/10.1021/acs.organomet.2c00344