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

Research output: Contribution to journalArticle

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 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.

Original languageEnglish
Pages (from-to)581-585
Number of pages5
JournalInorganica Chimica Acta
Volume363
Issue number3
DOIs
Publication statusPublished - Feb 15 2010

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Carbon Monoxide
Hydrides
Isomers
hydrides
isomers
Ligands
ligands
Bond length
Discrete Fourier transforms
Electronic structure
Crystal structure
electronic structure
operators
crystal structure
rings
Metals
metals

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Structural and computational studies of Cp(CO)2(PCy3)MoFBF3, a complex with a bound BF4 - ligand. / Cheng, Tan Yun; Szalda, David J.; Franz, James A.; Bullock, R Morris.

In: Inorganica Chimica Acta, Vol. 363, No. 3, 15.02.2010, p. 581-585.

Research output: Contribution to journalArticle

Cheng, Tan Yun ; Szalda, David J. ; Franz, James A. ; Bullock, R Morris. / Structural and computational studies of Cp(CO)2(PCy3)MoFBF3, a complex with a bound BF4 - ligand. In: Inorganica Chimica Acta. 2010 ; Vol. 363, No. 3. pp. 581-585.
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AU - Bullock, R Morris

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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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