High-resolution solid-state 13C NMR studies of chemisorbed organometallics. Chemisorptive formation of cation-like and alkylidene organotantalum complexes on high surface area inorganic oxides

Hongsang Ahn, Tobin J Marks

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Abstract

13C CPMAS NMR spectroscopy has been employed to investigate the surface chemistry of the organotantalum hydrocarbyl/alkylidene complexes, Cp′Ta(13CH3)4 (1*), Cp2Ta(13CH3)3 (2*), Cp2Ta(13CH2)-(13CH3) (3*), and Ta(13CHtBu)(13CH2t Bu)3 (4*) [Cp′ = η5-(CH3)5C5, Cp = η5-C5H5] supported on partially dehydroxylated silica (PDS), dehydroxylated silica (DS), or dehydroxylated γ-alumina (DA). Mono-Cp tantalum hydrocarbyl 1* undergoes chemisorption to form Cp′Ta(13CH3)3O-Si μ-oxo species on silica, and "cation-like" Cp′Ta(13CH3)3+ and Cp′Ta(13CH3)3O-Al μ-oxo species on DA, via pathways analogous to those established for organo-group 4 and actinide complexes. When supported on DA, bis-Cp tantalum hydrocarbyl 2* follows the same chemisorption mode as 1*. However, when 2* is chemisorbed on PDS and DS, a "cation-like" Cp2Ta(13CH3)2+ species is the major adsorbate product. On PDS, bis-Cp tantalum alkylidene complex 3* is converted predominantly to a stable "cation-like" Cp2Ta(13CH3)2+ species, presumably via electrophilic addition of a proton from the PDS surface. In contrast to 3*, Ta alkylidene complex 4* forms predominantly a Ta(13CHtBu)(13CH2t Bu)2O-Si, μ-oxo-alkylidene species on PDS.

Original languageEnglish
Pages (from-to)7103-7110
Number of pages8
JournalJournal of the American Chemical Society
Volume124
Issue number24
DOIs
Publication statusPublished - Jun 19 2002

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Organometallics
Silicon Dioxide
Oxides
Cations
Positive ions
Silica
Nuclear magnetic resonance
Tantalum
Aluminum Oxide
Alumina
Chemisorption
Actinoid Series Elements
Carbon-13 Magnetic Resonance Spectroscopy
Actinides
Adsorbates
Surface chemistry
Nuclear magnetic resonance spectroscopy
Protons
Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "High-resolution solid-state 13C NMR studies of chemisorbed organometallics. Chemisorptive formation of cation-like and alkylidene organotantalum complexes on high surface area inorganic oxides",
abstract = "13C CPMAS NMR spectroscopy has been employed to investigate the surface chemistry of the organotantalum hydrocarbyl/alkylidene complexes, Cp′Ta(13CH3)4 (1*), Cp2Ta(13CH3)3 (2*), Cp2Ta(13CH2)-(13CH3) (3*), and Ta(13CHtBu)(13CH2t Bu)3 (4*) [Cp′ = η5-(CH3)5C5, Cp = η5-C5H5] supported on partially dehydroxylated silica (PDS), dehydroxylated silica (DS), or dehydroxylated γ-alumina (DA). Mono-Cp tantalum hydrocarbyl 1* undergoes chemisorption to form Cp′Ta(13CH3)3O-Si μ-oxo species on silica, and {"}cation-like{"} Cp′Ta(13CH3)3+ and Cp′Ta(13CH3)3O-Al μ-oxo species on DA, via pathways analogous to those established for organo-group 4 and actinide complexes. When supported on DA, bis-Cp tantalum hydrocarbyl 2* follows the same chemisorption mode as 1*. However, when 2* is chemisorbed on PDS and DS, a {"}cation-like{"} Cp2Ta(13CH3)2+ species is the major adsorbate product. On PDS, bis-Cp tantalum alkylidene complex 3* is converted predominantly to a stable {"}cation-like{"} Cp2Ta(13CH3)2+ species, presumably via electrophilic addition of a proton from the PDS surface. In contrast to 3*, Ta alkylidene complex 4* forms predominantly a Ta(13CHtBu)(13CH2t Bu)2O-Si, μ-oxo-alkylidene species on PDS.",
author = "Hongsang Ahn and Marks, {Tobin J}",
year = "2002",
month = "6",
day = "19",
doi = "10.1021/ja0123204",
language = "English",
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pages = "7103--7110",
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T1 - High-resolution solid-state 13C NMR studies of chemisorbed organometallics. Chemisorptive formation of cation-like and alkylidene organotantalum complexes on high surface area inorganic oxides

AU - Ahn, Hongsang

AU - Marks, Tobin J

PY - 2002/6/19

Y1 - 2002/6/19

N2 - 13C CPMAS NMR spectroscopy has been employed to investigate the surface chemistry of the organotantalum hydrocarbyl/alkylidene complexes, Cp′Ta(13CH3)4 (1*), Cp2Ta(13CH3)3 (2*), Cp2Ta(13CH2)-(13CH3) (3*), and Ta(13CHtBu)(13CH2t Bu)3 (4*) [Cp′ = η5-(CH3)5C5, Cp = η5-C5H5] supported on partially dehydroxylated silica (PDS), dehydroxylated silica (DS), or dehydroxylated γ-alumina (DA). Mono-Cp tantalum hydrocarbyl 1* undergoes chemisorption to form Cp′Ta(13CH3)3O-Si μ-oxo species on silica, and "cation-like" Cp′Ta(13CH3)3+ and Cp′Ta(13CH3)3O-Al μ-oxo species on DA, via pathways analogous to those established for organo-group 4 and actinide complexes. When supported on DA, bis-Cp tantalum hydrocarbyl 2* follows the same chemisorption mode as 1*. However, when 2* is chemisorbed on PDS and DS, a "cation-like" Cp2Ta(13CH3)2+ species is the major adsorbate product. On PDS, bis-Cp tantalum alkylidene complex 3* is converted predominantly to a stable "cation-like" Cp2Ta(13CH3)2+ species, presumably via electrophilic addition of a proton from the PDS surface. In contrast to 3*, Ta alkylidene complex 4* forms predominantly a Ta(13CHtBu)(13CH2t Bu)2O-Si, μ-oxo-alkylidene species on PDS.

AB - 13C CPMAS NMR spectroscopy has been employed to investigate the surface chemistry of the organotantalum hydrocarbyl/alkylidene complexes, Cp′Ta(13CH3)4 (1*), Cp2Ta(13CH3)3 (2*), Cp2Ta(13CH2)-(13CH3) (3*), and Ta(13CHtBu)(13CH2t Bu)3 (4*) [Cp′ = η5-(CH3)5C5, Cp = η5-C5H5] supported on partially dehydroxylated silica (PDS), dehydroxylated silica (DS), or dehydroxylated γ-alumina (DA). Mono-Cp tantalum hydrocarbyl 1* undergoes chemisorption to form Cp′Ta(13CH3)3O-Si μ-oxo species on silica, and "cation-like" Cp′Ta(13CH3)3+ and Cp′Ta(13CH3)3O-Al μ-oxo species on DA, via pathways analogous to those established for organo-group 4 and actinide complexes. When supported on DA, bis-Cp tantalum hydrocarbyl 2* follows the same chemisorption mode as 1*. However, when 2* is chemisorbed on PDS and DS, a "cation-like" Cp2Ta(13CH3)2+ species is the major adsorbate product. On PDS, bis-Cp tantalum alkylidene complex 3* is converted predominantly to a stable "cation-like" Cp2Ta(13CH3)2+ species, presumably via electrophilic addition of a proton from the PDS surface. In contrast to 3*, Ta alkylidene complex 4* forms predominantly a Ta(13CHtBu)(13CH2t Bu)2O-Si, μ-oxo-alkylidene species on PDS.

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