Methane vs benzene activation via transient [sup t]Bu[sub 3]SiNHTa([double bond]NSi[sup t]Bu[sub 3])[sub 2]: Structure of (py)[sub 2]MeTa([double bond]NSi[sup t]Bu[sub 3])[sub 2]
- Cornell Univ., Ithaca, NY (United States)
Addition of Me[sub 3]TaCl[sub 2] to 2.0 equiv of LiNHSi[sup t]Bu[sub 3] in hexanes resulted in CH[sub 4] and ([sup t]Bu[sub 3]SiNH)Me[sub 2]Ta[double bond]NSi[sup t]Bu[sub 3] (1, 63%). Thermolysis of 1 in benzene resulted in disproportionation, but in pyridine and THF, L[sub 2]MeTa([double bond]NSi[sup t]Bu[sub 3])[sub 2] (L = py, 2(py)[sub 2], 68%; THF, 2(THF)[sub 2], 13%) and MeH were produced. Addition of TaCl[sub 5] to 4.0 equiv of LiNHSi[sup t]Bu[sub 3] in Et[sub 2]O at [minus]78[degrees]C afforded ([sup t]Bu[sub 3]SiNH)[sub 2]ClTa[double bond]NSi[sup t]Bu[sub 3] (3-Cl) [sup t]Bu[sub 3]SiNH[sub 2]. Alkylation of 3-Cl with AlMe[sub 3] (hexanes), PhLi (Et[sub 2]O/hexanes), PhCH[sub 2]K (toluene), and [sup t]BuCH[sub 2]Li(Et[sub 2]O) provided ([sup t]Bu[sub 3]SiNH)[sub 2]RTa[double bond]NSi[sup t]Bu[sub 3] (R = Me, 3-Me, 78%; Ph, 3-Ph, 64%; CH[sub 2]Ph, 3-CH[sub 2]Ph, 51%; CH[sub 2][sup t]Bu, 3-CH[sub 2][sup t]Bu, 39%). Addition of [sup t]Bu[sub 3]SiNH[sub 2] or [sup t]Bu[sub 3]SiOH to 1 yielded 3-Me or ([sup t]Bu[sub 3]SiNH)([sup t]Bu[sub 3]SiO)MeTa[double bond]NSi[sup t]Bu[sub 3] (5-Me, 52%) and CH[sub 4]. Thermolysis of 3-R effected 1,2-RH-elimination to form transient ([sup t]Bu[sub 3]SiNH)Ta([double bond]NSi[sup t]Bu[sub 3])[sub 2] (4), a species capable of adding C-H bonds across one imido linkage. Moderate rates of elimination from 3-R could be obtained only at 182.8 (4) [degrees]C.
- OSTI ID:
- 6769983
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:2; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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ALKANES
AROMATICS
BENZENE
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
COHERENT SCATTERING
DATA
DIFFRACTION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
LATTICE PARAMETERS
MAGNETIC RESONANCE
METHANE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHYSICAL PROPERTIES
REFRACTORY METAL COMPOUNDS
RESONANCE
SCATTERING
TANTALUM COMPOUNDS
THERMAL DEGRADATION
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION