Structural and computational studies of Cp(CO)2(PCy3)MoFBF3, a complex with a bound BF4- ligand

Tan Yun Cheng; David J. Szalda; James A. Franz; R. Morris Bullock

doi:10.1016/j.ica.2009.02.028

Structural and computational studies of Cp(CO)₂(PCy₃)MoFBF₃, a complex with a bound BF₄^- ligand

Tan Yun Cheng, David J. Szalda, James A. Franz, R. Morris Bullock

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

3 Citations (Scopus)

Abstract

Hydride transfer from Cp(CO)₂(PCy₃)MoH to Ph₃ C⁺ 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 Δ G_{g, 298}^{{ring operator}}) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)₂(PCy₃)MoH to Ph₃ C⁺ BAr₄^′- [Ar^′ = 3, 5 - bis(trifluoromethyl)phenyl] in CH₂Cl₂ solvent produces [Cp (CO)₂ (PCy₃) Mo (ClCH₂ Cl)]⁺ [BAr₄^′]^-, in which CH₂Cl₂ is coordinated to the metal.

Original language	English
Pages (from-to)	581-585
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	363
Issue number	3
DOIs	https://doi.org/10.1016/j.ica.2009.02.028
Publication status	Published - Feb 15 2010

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Keywords

DFT computations
Hydride transfer reactions
Metal hydride
Molybdenum complex
Weakly coordinating ligand

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Cite this

Cheng, T. Y., Szalda, D. J., Franz, J. A., & Morris Bullock, R. (2010). Structural and computational studies of Cp(CO)₂(PCy₃)MoFBF₃, a complex with a bound BF₄^- ligand. Inorganica Chimica Acta, 363(3), 581-585. https://doi.org/10.1016/j.ica.2009.02.028

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abstract = "Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3 C+ 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) {\AA}, which is 0.15 {\AA} 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 Δ Gg, 298{ring operator}) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3 C+ BAr4′- [Ar′ = 3, 5 - bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp (CO)2 (PCy3) Mo (ClCH2 Cl)]+ [BAr4′]-, in which CH2Cl2 is coordinated to the metal.",

keywords = "DFT computations, Hydride transfer reactions, Metal hydride, Molybdenum complex, Weakly coordinating ligand",

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AU - Morris Bullock, R.

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N2 - Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3 C+ 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 Δ Gg, 298{ring operator}) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3 C+ BAr4′- [Ar′ = 3, 5 - bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp (CO)2 (PCy3) Mo (ClCH2 Cl)]+ [BAr4′]-, in which CH2Cl2 is coordinated to the metal.

AB - Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3 C+ 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 Δ Gg, 298{ring operator}) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3 C+ BAr4′- [Ar′ = 3, 5 - bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp (CO)2 (PCy3) Mo (ClCH2 Cl)]+ [BAr4′]-, in which CH2Cl2 is coordinated to the metal.

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10.1016/j.ica.2009.02.028