Hydrogenation and silylation of a double-cyclometalated ruthenium complex: structures and dynamic behavior of hydrido and hydridosilicate ruthenium complexes
A double-cyclometalated ruthenium complex containing a chiral tripodal phospholane has been prepared by reaction with [Ru(η4-COD)(η3-methylallyl)2] via elimination of isobutene. The ruthenium-carbon bonds of this compound were reversibly cleaved by H2, resulting in an equilibrium between a tri- and...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
July 22, 2013
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| In: |
Organometallics
Year: 2013, Volume: 32, Issue: 15, Pages: 4409-4415 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om400574a |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/om400574a
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| Author Notes: | Peter Scherl, Hubert Wadepohl, and Lutz H. Gade |
| Summary: | A double-cyclometalated ruthenium complex containing a chiral tripodal phospholane has been prepared by reaction with [Ru(η4-COD)(η3-methylallyl)2] via elimination of isobutene. The ruthenium-carbon bonds of this compound were reversibly cleaved by H2, resulting in an equilibrium between a tri- and a tetrahydride (4 and 5). T1 relaxation time measurements revealed the nonclassical nature of the fluctuating hydrides. Release of the gas led to complete re-formation of the cyclometalated compound. Reaction of 3 with D2 afforded D10-5, in which six ortho-phenyl protons and four hydrides were replaced by deuterium. Furthermore, diphenylsilane was found to readily insert into one Ru-C bond to form 6, containing a κ3-dihydridosilicate fragment. On the basis of deuterium labeling experiments, the fast exchange between the two hydrides was shown to include a reductive elimination/oxidative addition step involving the remaining metalated phenyl group. Again, pressurization of 6 with H2 resulted in reversible cleavage of the remaining Ru-C bond, yielding the corresponding trihydride 7. |
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| Item Description: | Gesehen am 07.02.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om400574a |