Protonation of metal hydrides by strong acids. Formation of an equilibrium mixture of dihydride and dihydrogen complexes from protonation of Cp*Os(CO)2H. Structural characterization of [CpW(CO)2(PMe3)(H)2]+OTf-

R Morris Bullock, Jeong Sup Song, David J. Szalda

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Abstract

Cp*Os(CO)2H is protonated by triflic acid (HOTf) in CD2Cl2 solution to give an equilibrium mixture (87:13) of the dihydride [Cp*Os(CO)2(H)2]+OTf - and the dihydrogen complex [Cp*Os-(CO)22-H2)] +OTf-. The acidity of these protonated species is roughly comparable to HOTf, since only partial protonation was observed, e.g., 36% protonation with 1.2 equiv of HOTf. In the absence of acid, the T1 of the hydride ligand of Cp*Os(CO)2H is 5.9 s at -80°C. When all of the Cp*Os(CO)2H is protonated by excess HOTf, the T1 (-80°C) of the terminal hydride ligands of [Cp*Os(CO)2(H)2]+OTf- is 2.8 s, while the T1 of the dihydrogen ligand of [Cp*Os(CO)22-H2)] +OTf- is 19 ms (-80°C). The observed T1 values of the Os-H resonance of Cp*Os(CO)2H decreased significantly under conditions of partial protonation, indicating intermolecular proton transfer among [Cp*Os(CO)22-H2)] +OTf-, [Cp*Os(CO)2(H)2]+OTf-, Cp*Os(CO)2H, and HOTf. IR spectra indicate that the two CO ligands of [Cp*Os(CO)2(H)2]+ (and hence the hydrides as well) are trans to each other in the four-legged piano stool geometry. Two resonances for HOTf are observed in the NMR spectra and are assigned as [HOTf]n (hydrogen bonded to itself) and TfOH⋯OTf- in which HOTf is hydrogen bonded to an OTf- counterion. [CpW(CO)3(H)2]+OTf- and [Cp*W(CO)3(H)2]+OTf- were formed by protonation of CpW(CO)3H and Cp*W(CO)3H. Protonation of the phosphine-substituted tungsten hydrides CpW(CO)2(PR3)H (R = Me, Cy, Ph) by HOTf or [H(Et2O)2]+ BAr′4 - (Ar′ = 3,5-bis(trifluoromethyl)phenyl) gives dihydrides [CpW(CO)2(PR3)(H)2]+ which were isolated and fully characterized. The structure of [CpW(CO)2(PMe3)(H)2]+OTf- was determined by single-crystal X-ray diffraction and reveals weak hydrogen bonds between one hydride on W and two of the fluorines on the triflate anion.

Original languageEnglish
Pages (from-to)2504-2516
Number of pages13
JournalOrganometallics
Volume15
Issue number10
Publication statusPublished - May 14 1996

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dihydrides
metal hydrides
Protonation
Hydrides
hydrides
Metals
acids
Acids
Ligands
ligands
phosphine
Hydrogen
Tungsten
Proton transfer
Fluorine
hydrogen
phosphines
Acidity
acidity
Anions

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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@article{77069776f2ce4ba2a2e3e49d17a32800,
title = "Protonation of metal hydrides by strong acids. Formation of an equilibrium mixture of dihydride and dihydrogen complexes from protonation of Cp*Os(CO)2H. Structural characterization of [CpW(CO)2(PMe3)(H)2]+OTf-",
abstract = "Cp*Os(CO)2H is protonated by triflic acid (HOTf) in CD2Cl2 solution to give an equilibrium mixture (87:13) of the dihydride [Cp*Os(CO)2(H)2]+OTf - and the dihydrogen complex [Cp*Os-(CO)2(η2-H2)] +OTf-. The acidity of these protonated species is roughly comparable to HOTf, since only partial protonation was observed, e.g., 36{\%} protonation with 1.2 equiv of HOTf. In the absence of acid, the T1 of the hydride ligand of Cp*Os(CO)2H is 5.9 s at -80°C. When all of the Cp*Os(CO)2H is protonated by excess HOTf, the T1 (-80°C) of the terminal hydride ligands of [Cp*Os(CO)2(H)2]+OTf- is 2.8 s, while the T1 of the dihydrogen ligand of [Cp*Os(CO)2(η2-H2)] +OTf- is 19 ms (-80°C). The observed T1 values of the Os-H resonance of Cp*Os(CO)2H decreased significantly under conditions of partial protonation, indicating intermolecular proton transfer among [Cp*Os(CO)2(η2-H2)] +OTf-, [Cp*Os(CO)2(H)2]+OTf-, Cp*Os(CO)2H, and HOTf. IR spectra indicate that the two CO ligands of [Cp*Os(CO)2(H)2]+ (and hence the hydrides as well) are trans to each other in the four-legged piano stool geometry. Two resonances for HOTf are observed in the NMR spectra and are assigned as [HOTf]n (hydrogen bonded to itself) and TfOH⋯OTf- in which HOTf is hydrogen bonded to an OTf- counterion. [CpW(CO)3(H)2]+OTf- and [Cp*W(CO)3(H)2]+OTf- were formed by protonation of CpW(CO)3H and Cp*W(CO)3H. Protonation of the phosphine-substituted tungsten hydrides CpW(CO)2(PR3)H (R = Me, Cy, Ph) by HOTf or [H(Et2O)2]+ BAr′4 - (Ar′ = 3,5-bis(trifluoromethyl)phenyl) gives dihydrides [CpW(CO)2(PR3)(H)2]+ which were isolated and fully characterized. The structure of [CpW(CO)2(PMe3)(H)2]+OTf- was determined by single-crystal X-ray diffraction and reveals weak hydrogen bonds between one hydride on W and two of the fluorines on the triflate anion.",
author = "Bullock, {R Morris} and Song, {Jeong Sup} and Szalda, {David J.}",
year = "1996",
month = "5",
day = "14",
language = "English",
volume = "15",
pages = "2504--2516",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Protonation of metal hydrides by strong acids. Formation of an equilibrium mixture of dihydride and dihydrogen complexes from protonation of Cp*Os(CO)2H. Structural characterization of [CpW(CO)2(PMe3)(H)2]+OTf-

AU - Bullock, R Morris

AU - Song, Jeong Sup

AU - Szalda, David J.

PY - 1996/5/14

Y1 - 1996/5/14

N2 - Cp*Os(CO)2H is protonated by triflic acid (HOTf) in CD2Cl2 solution to give an equilibrium mixture (87:13) of the dihydride [Cp*Os(CO)2(H)2]+OTf - and the dihydrogen complex [Cp*Os-(CO)2(η2-H2)] +OTf-. The acidity of these protonated species is roughly comparable to HOTf, since only partial protonation was observed, e.g., 36% protonation with 1.2 equiv of HOTf. In the absence of acid, the T1 of the hydride ligand of Cp*Os(CO)2H is 5.9 s at -80°C. When all of the Cp*Os(CO)2H is protonated by excess HOTf, the T1 (-80°C) of the terminal hydride ligands of [Cp*Os(CO)2(H)2]+OTf- is 2.8 s, while the T1 of the dihydrogen ligand of [Cp*Os(CO)2(η2-H2)] +OTf- is 19 ms (-80°C). The observed T1 values of the Os-H resonance of Cp*Os(CO)2H decreased significantly under conditions of partial protonation, indicating intermolecular proton transfer among [Cp*Os(CO)2(η2-H2)] +OTf-, [Cp*Os(CO)2(H)2]+OTf-, Cp*Os(CO)2H, and HOTf. IR spectra indicate that the two CO ligands of [Cp*Os(CO)2(H)2]+ (and hence the hydrides as well) are trans to each other in the four-legged piano stool geometry. Two resonances for HOTf are observed in the NMR spectra and are assigned as [HOTf]n (hydrogen bonded to itself) and TfOH⋯OTf- in which HOTf is hydrogen bonded to an OTf- counterion. [CpW(CO)3(H)2]+OTf- and [Cp*W(CO)3(H)2]+OTf- were formed by protonation of CpW(CO)3H and Cp*W(CO)3H. Protonation of the phosphine-substituted tungsten hydrides CpW(CO)2(PR3)H (R = Me, Cy, Ph) by HOTf or [H(Et2O)2]+ BAr′4 - (Ar′ = 3,5-bis(trifluoromethyl)phenyl) gives dihydrides [CpW(CO)2(PR3)(H)2]+ which were isolated and fully characterized. The structure of [CpW(CO)2(PMe3)(H)2]+OTf- was determined by single-crystal X-ray diffraction and reveals weak hydrogen bonds between one hydride on W and two of the fluorines on the triflate anion.

AB - Cp*Os(CO)2H is protonated by triflic acid (HOTf) in CD2Cl2 solution to give an equilibrium mixture (87:13) of the dihydride [Cp*Os(CO)2(H)2]+OTf - and the dihydrogen complex [Cp*Os-(CO)2(η2-H2)] +OTf-. The acidity of these protonated species is roughly comparable to HOTf, since only partial protonation was observed, e.g., 36% protonation with 1.2 equiv of HOTf. In the absence of acid, the T1 of the hydride ligand of Cp*Os(CO)2H is 5.9 s at -80°C. When all of the Cp*Os(CO)2H is protonated by excess HOTf, the T1 (-80°C) of the terminal hydride ligands of [Cp*Os(CO)2(H)2]+OTf- is 2.8 s, while the T1 of the dihydrogen ligand of [Cp*Os(CO)2(η2-H2)] +OTf- is 19 ms (-80°C). The observed T1 values of the Os-H resonance of Cp*Os(CO)2H decreased significantly under conditions of partial protonation, indicating intermolecular proton transfer among [Cp*Os(CO)2(η2-H2)] +OTf-, [Cp*Os(CO)2(H)2]+OTf-, Cp*Os(CO)2H, and HOTf. IR spectra indicate that the two CO ligands of [Cp*Os(CO)2(H)2]+ (and hence the hydrides as well) are trans to each other in the four-legged piano stool geometry. Two resonances for HOTf are observed in the NMR spectra and are assigned as [HOTf]n (hydrogen bonded to itself) and TfOH⋯OTf- in which HOTf is hydrogen bonded to an OTf- counterion. [CpW(CO)3(H)2]+OTf- and [Cp*W(CO)3(H)2]+OTf- were formed by protonation of CpW(CO)3H and Cp*W(CO)3H. Protonation of the phosphine-substituted tungsten hydrides CpW(CO)2(PR3)H (R = Me, Cy, Ph) by HOTf or [H(Et2O)2]+ BAr′4 - (Ar′ = 3,5-bis(trifluoromethyl)phenyl) gives dihydrides [CpW(CO)2(PR3)(H)2]+ which were isolated and fully characterized. The structure of [CpW(CO)2(PMe3)(H)2]+OTf- was determined by single-crystal X-ray diffraction and reveals weak hydrogen bonds between one hydride on W and two of the fluorines on the triflate anion.

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