Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 130, Issue 49, Pages 16729-16738Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja8070072
Keywords
-
Categories
Funding
- CNRS
- UPS
- ANR programs
- NSF [CHE-0517798, CHE-0521047, FG0286ER13615]
- Sloan Foundation
- Dreyfus Foundation
- Petroleum Research Fund
Ask authors/readers for more resources
The ambiphilic triphosphine-borane ligand 1 {TPB = [o-iPr(2)P-(C6H4)](3)B} readily coordinates to all group 10 and 11 metals to afford a complete series of metal boratranes (TPB)[M] 2-8 (2: M = Ni, 3: M = Pd, 4: M = Pt, 5: M = CuCl, 6: M = AgCl, 7: M = AuCl, 8: M = Au+). Spectroscopic and structural characterization unambiguously establishes the presence of M -> B interactions in all of these complexes. The first evidence for borane coordination to copper and silver is provided, and the Au -> B interaction is shown to persist upon chloride abstraction. Experimental and theoretical considerations indicate that the M -> B interaction is strongest in the Pt and Au complexes. The influence of the oxidation state and charge of the metal is substantiated, and the consequences of relativistic effects are discussed. The coordination of the a-acceptor borane ligand is found to induce a significant bathochromic shift of the UV-vis spectra, the Ni, Pd, and Pt complex presenting strong absorptions in the visible range. In addition, all of the group 10 and 11 metal boratranes adopt C-3 symmetry both in the solid state and in solution. The central M -> B interaction is found to moderately influence the degree of helicity and configurational stability of these three-bladed propellers, and DFT calculations support a dissociative pathway for the inversion process.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available