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 › peer-review

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

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

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@article{aa6c7f3324164b2a993f6286c10266f9,

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

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",

author = "Cheng, {Tan Yun} and Szalda, {David J.} and Franz, {James A.} and {Morris Bullock}, R.",

year = "2010",

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doi = "10.1016/j.ica.2009.02.028",

language = "English",

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pages = "581--585",

journal = "Inorganica Chimica Acta",

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T1 - Structural and computational studies of Cp(CO)2(PCy3)MoFBF3, a complex with a bound BF4- ligand

AU - Cheng, Tan Yun

AU - Szalda, David J.

AU - Franz, James A.

AU - Morris Bullock, R.

PY - 2010/2/15

Y1 - 2010/2/15

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.

KW - DFT computations

KW - Hydride transfer reactions

KW - Metal hydride

KW - Molybdenum complex

KW - Weakly coordinating ligand

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