Phosphinoborane-induced fragmentation of the unsaturated hydride H2Re2(CO)8
- University of North Texas
- ORNL
The reactivity of the unsaturated dimer H{sub 2}Re{sub 2}(CO){sub 8} (1) with the ambiphilic phosphinoborane Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (2; where BR{sub 2} = 9-borabicyclo[3.3.1]nonanyl) has been explored. Coordination of the ambiphilic ligand to 1 is rapid at room temperature, leading to the fragmentation of 1 and formation of HRe(CO){sub 4}({kappa}B,P-Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2}) (3) in high yield. 3 has been characterized in solution by IR and NMR spectroscopy, and the molecular structure established by X-ray diffraction analysis. The solid-state structure confirms the presence of a chelated phosphinoborane ligand through coordination of the phosphine to the rhenium center and the formation of a three-center, two-electron (3c,2e) Re-H-B interaction. The nature of the Re-H-B interaction in 3 has been investigated by DFT, and the energetics for borane dissociation and hydride abstraction by the coordinated Lewis acid in 3 have also been computationally evaluated. The coordination of an oxygen in one of the ancillary CO groups by the pendant borane in HRe(CO){sub 4}({kappa}P-Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2}) is thermodynamically unfavorable relative to the formation of the 3c,2e Re-H-B bond.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- DE-AC05-00OR22725
- OSTI ID:
- 1034012
- Journal Information:
- Journal of Organometallic Chemistry, Vol. 700; ISSN 0022-368X
- Country of Publication:
- United States
- Language:
- English
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