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. ISSN 0276-7333

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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 > 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
Date:	8 November 2010
Volume:	Vol.29
Number:	No.21
Page Range:	pp. 5591-5595
Identification Number:	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)
URI:	http://wrap.warwick.ac.uk/id/eprint/40511

Data sourced from Thomson Reuters' Web of Knowledge

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