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Structural and Computational Studies of Cp(CO)2(PCy3)MoFBF3, a Complex with a Bound BF4- Ligand

Journal Article · · Inorganica Chimica Acta, 363(3):581-585

Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BF4 gives Cp(CO)2(PCy3)MoFBF3, and the crystal structure of this complex was determined. In the weakly bound FBF3 ligand, the B-F(bridging) bond length is 1.475(8) Å, which is 0.15 Å longer than the average length of the three B-F(terminal) bonds. The PCy3 and FBF3 ligands are cis to each other in the four-legged piano stool structure. Electronic structure (DFT) calculations predict the trans isomer of Cp(CO)2(PCy3)MoFBF3 to be 9.5 kcal/mol (in ΔGog,298)) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BAr'4 [Ar' = 3,5-bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp(CO)2(PCy3)Mo(ClCH2Cl)]+[BAr'4] , in which CH2Cl2 is coordinated to the metal. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
978930
Report Number(s):
PNNL-SA-63229; KC0302010
Journal Information:
Inorganica Chimica Acta, 363(3):581-585, Journal Name: Inorganica Chimica Acta, 363(3):581-585 Journal Issue: 3 Vol. 363; ISSN 0020-1693; ISSN ICHAA3
Country of Publication:
United States
Language:
English