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Ruthenium, rhodium, and iridium bis(σ-B−H) diisopropylaminoborane complexes
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Alcaraz, Gilles, Chaplin, Adrian B., Stevens, Charlotte J., Clot, Eric, Vendier, Laure, Weller, Andrew S. and Sabo-Etienne, Sylviane (2010) Ruthenium, rhodium, and iridium bis(σ-B−H) diisopropylaminoborane complexes. Organometallics, Vol.29 (No.21). pp. 5591-5595. doi:10.1021/om1004995 ISSN 0276-7333.
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Official URL: http://dx.doi.org/10.1021/om1004995
Abstract
The coordination chemistry of diisopropylaminoborane H(2)B-N(i)Pr(2) with valence isoelectronic metal fragments to form, essentially isostructural, [MH(2)(eta(2):eta(2)-H(2)B-N(i)Pr(2))(PCy(3))(2)](n+) (M = Ru, n = 0; Rh and Ir, n = 1) has been explored by a combination of X-ray crystallography, NMR spectroscopy, and computational techniques. In the solid state and solution the aminoborane interacts with the metal centers through one four-center four-electron interaction, forming bis(sigma-B-H) complexes. The structural data point to tighter interactions between both the Ru and Ir congeners compared to the Rh with significantly shorter M center dot center dot center dot B distances in the first two. These tighter interactions are mirrored in the spectroscopic data, with the Ru and Ir complexes showing more deshielded (11)B chemical shifts and (1)H M-H-B resonances that are more shielded than observed for the rhodium complex. Analysis of the bonding between metal and bonnie using the NBO approach is in very good agreement with the variations in the geometrical and spectroscopic parameters. There is overall a stronger interaction between the borane and the metal fragment for neutral Ru compared to cationic Rh, with cationic Ir in an intermediate situation.
| Item Type: | Journal Article | ||||
|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Ruthenium, Rhodium, Iridium, Coordination compounds, Organometallic compounds | ||||
| Journal or Publication Title: | Organometallics | ||||
| Publisher: | American Chemical Society | ||||
| ISSN: | 0276-7333 | ||||
| Official Date: | 8 November 2010 | ||||
| Dates: |
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| Volume: | Vol.29 | ||||
| Number: | No.21 | ||||
| Page Range: | pp. 5591-5595 | ||||
| DOI: | 10.1021/om1004995 | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access | ||||
| Funder: | Centre national de la recherche scientifique (France) (CNRS), France. Agence nationale de la recherche (ANR), Université de Toulouse, University of Oxford | ||||
| Grant number: | ANR-09-BLAN-0184-01 HyBoCat (ANR) |
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