Photochemical Oxidative Addition of Germane and Diphenylgermane to Ruthenium Dihydride Complexes
In: Organometallics Organometallics, American Chemical Society, 2019, 38 (3), pp.626-637. ⟨10.1021/acs.organomet.8b00770⟩; (2019-01-25)
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Zugriff:
Photochemical reactions of germane and diphenylgermane with Ru(PP) 2 H 2 (PP = R 2 PCH 2 CH 2 PR 2 or DuPhos, R = Ph dppe, R = Et depe, R = Me dmpe) are reported. Reaction with GeH 4 generates a mixture of cis and trans isomers of Ru(PP) 2 (GeH 3 )H except for the DuPhos complex which yields the product only in the cis form. In situ laser photolysis (355 nm) demonstrates that the initial product is the cis isomer that undergoes thermal isomerization to the trans isomer. The complex cis-[Ru(dppe) 2 (GeH 3 )H] crystallizes selectively, allowing determination of its X-ray structure as a germyl hydride with a long Ru-H···Ge separation of 2.64(3) Å indicating that no residual interaction between the RuH and Ge is present. DFT calculations are also consistent with full oxidative addition. The structure of cis-[Ru(DuPhos) 2 (GeH 3 )H] reveals significant distortion from an octahedral geometry. The major species in the crystal (95%) exhibits a structure with a Ru-H···Ge distance of 2.42(5) Å suggesting negligible interaction between these centers. DFT calculations of the structure are consistent with the experimental determination. The reactions of Ru(PP) 2 H 2 with diphenylgermane yield cis-[Ru(PP) 2 (GePh 2 H)H] exclusively for PP = dmpe and depe, while the cis isomer is dominant in the case of dppe. A photochemical competition reaction between Ru(dppe) 2 (H) 2 and the two substrates Ph 2 SiH 2 and Ph 2 GeH 2 results in both Si-H and Ge-H oxidative addition activation with a kinetic preference (0.18:1) for the germyl hydride product. Thermal conversion of Ru(dppe) 2 (SiPh 2 H)H to Ru(dppe) 2 (GePh 2 H)H is observed on heating.
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Photochemical Oxidative Addition of Germane and Diphenylgermane to Ruthenium Dihydride Complexes
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Autor/in / Beteiligte Person: | Kendall, Hannah ; Sabo-Etienne, Sylviane ; Smart, Katharine A. ; Whitwood, Adrian C. ; Grellier, Mary ; Perutz, Robin N. ; Evans, Simon W. ; Dickinson, David ; Procacci, Barbara ; Department of Economics ; Appalachian State University ; University of North Carolina System (UNC)-University of North Carolina System (UNC) ; Laboratoire de chimie de coordination (LCC) ; Institut National Polytechnique (Toulouse) (Toulouse INP) ; Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3) ; Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599) ; Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3) ; Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) ; Department of Chemistry [York, UK] ; University of York [York, UK] ; EPSRC ; CNRS ; MENESR |
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Quelle: | Organometallics Organometallics, American Chemical Society, 2019, 38 (3), pp.626-637. ⟨10.1021/acs.organomet.8b00770⟩; (2019-01-25) |
Veröffentlichung: | HAL CCSD, 2019 |
Medientyp: | unknown |
ISSN: | 0276-7333 (print) ; 1520-6041 (print) |
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