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.",

note = "Funding Information: Research at Brookhaven National Laboratory was carried out under contract DE-AC02-98CH10886 with the US Department of Energy and was supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. Research at Pacific Northwest National Laboratory was funded by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. The provision of computing resources at the National Energy Research Scientific Computing Center (NERSC), Office of Science, US-DOE, at Lawrence Berkeley National Laboratory, is gratefully acknowledged. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "2010",

month = feb,

day = "15",

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

language = "English",

volume = "363",

pages = "581--585",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

number = "3",

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TY - JOUR

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.

N1 - Funding Information: Research at Brookhaven National Laboratory was carried out under contract DE-AC02-98CH10886 with the US Department of Energy and was supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. Research at Pacific Northwest National Laboratory was funded by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. The provision of computing resources at the National Energy Research Scientific Computing Center (NERSC), Office of Science, US-DOE, at Lawrence Berkeley National Laboratory, is gratefully acknowledged. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

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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U2 - 10.1016/j.ica.2009.02.028

DO - 10.1016/j.ica.2009.02.028

M3 - Article

AN - SCOPUS:75749132435

VL - 363

SP - 581

EP - 585

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

IS - 3

ER -