Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-

Stephen W. Kirtley, Mark A. Andrews, Robert Bau, Gregory W. Grynkewich, Tobin J. Marks, Tobin J Marks, Bruce R. Whittlesey

Research output: Contribution to journalArticle

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Abstract

The compound [(Ph3P)2N] [Mo(CO)4BH4] can be prepared in 25% yield by the reaction of [(Ph3P)2N| [Mo(CO)51] and [(Ph3P)2N][BH4] in anhydrous tetrahydrofuran. Mechanistic studies show that iodide ion acts as a catalyst in the synthesis. X-ray diffraction studies reveal that the compound crystallizes in the space group P1̄ (a = 17.828 (8) Å, b = 9.714 (4) Å, c = 12.371 (5)Å, α = 101.77(1)°, β = 115.36 (1)°, γ = 94.40 (1)°, V = 1886.9 Å3, ρobsd = 1.33 g cm-3, ρcalcd = 1.34 g cm-3 for Z = 2). Data were collected with Zr-filtered Mo Kα radiation to a 2θ limit of 45°. Standard Patterson, Fourier, and least-squares techniques resulted in final agreement factors: R = 8.3%, Rw = 8.1% for 3208 reflections with I > 3σ. The tetrahydroborate ligand is attached to the metal via two Mo-H-B bridge bonds with Mo-Hb = 2.02 (8) Å. The coordination about the central molybdenum atom is approximately octahedral, but two notable distortions occur in the equatorial plane: C(eq)-Mo-C(eq) = 84.5 (5)° and Hb-Mo-Hb = 59 (4)°. The geometry about the boron is virtually tetrahedral, with Mo-B = 2.41 (2) Å. The ligational analogy between μ3-allyl and BH4- is further strengthened by the results of this study. Boron-decoupled 1H NMR spectra reveal that bridge-terminal hydrogen interchange occurs within the tetrahydroborate ligand with ΔGcDagger = 10.0 ± 0.2 kcal/mol. As revealed by 13C NMR studies, this rearrangement process is not coupled to axial-equatorial CO exchange about the molybdenum coordination polyhedron; ΔCG‡ ≥ 18.6 kcal/mol for this process. This result places significant restrictions on operational BH4- rearrangement mechanisms. These are discussed in the light of a permutational analysis of differentiable rearrangement modes in covalent metal tetrahydroborates.

Original languageEnglish
Pages (from-to)7154-7162
Number of pages9
JournalJournal of the American Chemical Society
Volume99
Issue number22
Publication statusPublished - 1977

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Molecular Dynamics Simulation
Carbon Monoxide
Molybdenum
Anions
Boron
Molecular dynamics
Negative ions
Ligands
Nuclear magnetic resonance
Interchanges
Metals
R Factors
Iodides
Least-Squares Analysis
Radiation
X-Ray Diffraction
X ray diffraction
Atoms
Hydrogen
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Kirtley, S. W., Andrews, M. A., Bau, R., Grynkewich, G. W., Marks, T. J., Marks, T. J., & Whittlesey, B. R. (1977). Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-. Journal of the American Chemical Society, 99(22), 7154-7162.

Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-. / Kirtley, Stephen W.; Andrews, Mark A.; Bau, Robert; Grynkewich, Gregory W.; Marks, Tobin J.; Marks, Tobin J; Whittlesey, Bruce R.

In: Journal of the American Chemical Society, Vol. 99, No. 22, 1977, p. 7154-7162.

Research output: Contribution to journalArticle

Kirtley, SW, Andrews, MA, Bau, R, Grynkewich, GW, Marks, TJ, Marks, TJ & Whittlesey, BR 1977, 'Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-', Journal of the American Chemical Society, vol. 99, no. 22, pp. 7154-7162.
Kirtley, Stephen W. ; Andrews, Mark A. ; Bau, Robert ; Grynkewich, Gregory W. ; Marks, Tobin J. ; Marks, Tobin J ; Whittlesey, Bruce R. / Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-. In: Journal of the American Chemical Society. 1977 ; Vol. 99, No. 22. pp. 7154-7162.
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title = "Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-",
abstract = "The compound [(Ph3P)2N] [Mo(CO)4BH4] can be prepared in 25{\%} yield by the reaction of [(Ph3P)2N| [Mo(CO)51] and [(Ph3P)2N][BH4] in anhydrous tetrahydrofuran. Mechanistic studies show that iodide ion acts as a catalyst in the synthesis. X-ray diffraction studies reveal that the compound crystallizes in the space group P1̄ (a = 17.828 (8) {\AA}, b = 9.714 (4) {\AA}, c = 12.371 (5){\AA}, α = 101.77(1)°, β = 115.36 (1)°, γ = 94.40 (1)°, V = 1886.9 {\AA}3, ρobsd = 1.33 g cm-3, ρcalcd = 1.34 g cm-3 for Z = 2). Data were collected with Zr-filtered Mo Kα radiation to a 2θ limit of 45°. Standard Patterson, Fourier, and least-squares techniques resulted in final agreement factors: R = 8.3{\%}, Rw = 8.1{\%} for 3208 reflections with I > 3σ. The tetrahydroborate ligand is attached to the metal via two Mo-H-B bridge bonds with Mo-Hb = 2.02 (8) {\AA}. The coordination about the central molybdenum atom is approximately octahedral, but two notable distortions occur in the equatorial plane: C(eq)-Mo-C(eq) = 84.5 (5)° and Hb-Mo-Hb = 59 (4)°. The geometry about the boron is virtually tetrahedral, with Mo-B = 2.41 (2) {\AA}. The ligational analogy between μ3-allyl and BH4- is further strengthened by the results of this study. Boron-decoupled 1H NMR spectra reveal that bridge-terminal hydrogen interchange occurs within the tetrahydroborate ligand with ΔGcDagger = 10.0 ± 0.2 kcal/mol. As revealed by 13C NMR studies, this rearrangement process is not coupled to axial-equatorial CO exchange about the molybdenum coordination polyhedron; ΔCG‡ ≥ 18.6 kcal/mol for this process. This result places significant restrictions on operational BH4- rearrangement mechanisms. These are discussed in the light of a permutational analysis of differentiable rearrangement modes in covalent metal tetrahydroborates.",
author = "Kirtley, {Stephen W.} and Andrews, {Mark A.} and Robert Bau and Grynkewich, {Gregory W.} and Marks, {Tobin J.} and Marks, {Tobin J} and Whittlesey, {Bruce R.}",
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T1 - Chemistry, structure, and molecular dynamics of the tetrahydroboratotetracarbonylmolybdate( 1 -) anion, Mo(CO)4BH4-

AU - Kirtley, Stephen W.

AU - Andrews, Mark A.

AU - Bau, Robert

AU - Grynkewich, Gregory W.

AU - Marks, Tobin J.

AU - Marks, Tobin J

AU - Whittlesey, Bruce R.

PY - 1977

Y1 - 1977

N2 - The compound [(Ph3P)2N] [Mo(CO)4BH4] can be prepared in 25% yield by the reaction of [(Ph3P)2N| [Mo(CO)51] and [(Ph3P)2N][BH4] in anhydrous tetrahydrofuran. Mechanistic studies show that iodide ion acts as a catalyst in the synthesis. X-ray diffraction studies reveal that the compound crystallizes in the space group P1̄ (a = 17.828 (8) Å, b = 9.714 (4) Å, c = 12.371 (5)Å, α = 101.77(1)°, β = 115.36 (1)°, γ = 94.40 (1)°, V = 1886.9 Å3, ρobsd = 1.33 g cm-3, ρcalcd = 1.34 g cm-3 for Z = 2). Data were collected with Zr-filtered Mo Kα radiation to a 2θ limit of 45°. Standard Patterson, Fourier, and least-squares techniques resulted in final agreement factors: R = 8.3%, Rw = 8.1% for 3208 reflections with I > 3σ. The tetrahydroborate ligand is attached to the metal via two Mo-H-B bridge bonds with Mo-Hb = 2.02 (8) Å. The coordination about the central molybdenum atom is approximately octahedral, but two notable distortions occur in the equatorial plane: C(eq)-Mo-C(eq) = 84.5 (5)° and Hb-Mo-Hb = 59 (4)°. The geometry about the boron is virtually tetrahedral, with Mo-B = 2.41 (2) Å. The ligational analogy between μ3-allyl and BH4- is further strengthened by the results of this study. Boron-decoupled 1H NMR spectra reveal that bridge-terminal hydrogen interchange occurs within the tetrahydroborate ligand with ΔGcDagger = 10.0 ± 0.2 kcal/mol. As revealed by 13C NMR studies, this rearrangement process is not coupled to axial-equatorial CO exchange about the molybdenum coordination polyhedron; ΔCG‡ ≥ 18.6 kcal/mol for this process. This result places significant restrictions on operational BH4- rearrangement mechanisms. These are discussed in the light of a permutational analysis of differentiable rearrangement modes in covalent metal tetrahydroborates.

AB - The compound [(Ph3P)2N] [Mo(CO)4BH4] can be prepared in 25% yield by the reaction of [(Ph3P)2N| [Mo(CO)51] and [(Ph3P)2N][BH4] in anhydrous tetrahydrofuran. Mechanistic studies show that iodide ion acts as a catalyst in the synthesis. X-ray diffraction studies reveal that the compound crystallizes in the space group P1̄ (a = 17.828 (8) Å, b = 9.714 (4) Å, c = 12.371 (5)Å, α = 101.77(1)°, β = 115.36 (1)°, γ = 94.40 (1)°, V = 1886.9 Å3, ρobsd = 1.33 g cm-3, ρcalcd = 1.34 g cm-3 for Z = 2). Data were collected with Zr-filtered Mo Kα radiation to a 2θ limit of 45°. Standard Patterson, Fourier, and least-squares techniques resulted in final agreement factors: R = 8.3%, Rw = 8.1% for 3208 reflections with I > 3σ. The tetrahydroborate ligand is attached to the metal via two Mo-H-B bridge bonds with Mo-Hb = 2.02 (8) Å. The coordination about the central molybdenum atom is approximately octahedral, but two notable distortions occur in the equatorial plane: C(eq)-Mo-C(eq) = 84.5 (5)° and Hb-Mo-Hb = 59 (4)°. The geometry about the boron is virtually tetrahedral, with Mo-B = 2.41 (2) Å. The ligational analogy between μ3-allyl and BH4- is further strengthened by the results of this study. Boron-decoupled 1H NMR spectra reveal that bridge-terminal hydrogen interchange occurs within the tetrahydroborate ligand with ΔGcDagger = 10.0 ± 0.2 kcal/mol. As revealed by 13C NMR studies, this rearrangement process is not coupled to axial-equatorial CO exchange about the molybdenum coordination polyhedron; ΔCG‡ ≥ 18.6 kcal/mol for this process. This result places significant restrictions on operational BH4- rearrangement mechanisms. These are discussed in the light of a permutational analysis of differentiable rearrangement modes in covalent metal tetrahydroborates.

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