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Title: 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]

Abstract

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 obtainedmore » only at 182.8 (4) [degrees]C.« less

Authors:
;  [1]
  1. (Cornell Univ., Ithaca, NY (United States))
Publication Date:
OSTI Identifier:
6769983
Alternate Identifier(s):
OSTI ID: 6769983
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; (United States); Journal Volume: 32:2
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 10 SYNTHETIC FUELS; 02 PETROLEUM; 03 NATURAL GAS; BENZENE; CHEMICAL ACTIVATION; METHANE; TANTALUM COMPOUNDS; CHEMICAL REACTIONS; EXPERIMENTAL DATA; LATTICE PARAMETERS; NUCLEAR MAGNETIC RESONANCE; ORGANOMETALLIC COMPOUNDS; THERMAL DEGRADATION; THERMODYNAMIC PROPERTIES; X-RAY DIFFRACTION; ALKANES; AROMATICS; COHERENT SCATTERING; DATA; DIFFRACTION; HYDROCARBONS; INFORMATION; MAGNETIC RESONANCE; NUMERICAL DATA; ORGANIC COMPOUNDS; PHYSICAL PROPERTIES; REFRACTORY METAL COMPOUNDS; RESONANCE; SCATTERING; TRANSITION ELEMENT COMPOUNDS 400201* -- Chemical & Physicochemical Properties; 100200 -- Synthetic Fuels-- Production-- (1990-); 020400 -- Petroleum-- Processing; 030300 -- Natural Gas-- Drilling, Production, & Processing

Citation Formats

Schaller, C.P., and Wolczanski, P.T.. 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]. United States: N. p., 1993. Web. doi:10.1021/ic00054a005.
Schaller, C.P., & Wolczanski, P.T.. 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]. United States. doi:10.1021/ic00054a005.
Schaller, C.P., and Wolczanski, P.T.. Wed . "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]". United States. doi:10.1021/ic00054a005.
@article{osti_6769983,
title = {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]},
author = {Schaller, C.P. and Wolczanski, P.T.},
abstractNote = {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.},
doi = {10.1021/ic00054a005},
journal = {Inorganic Chemistry; (United States)},
number = ,
volume = 32:2,
place = {United States},
year = {Wed Jan 20 00:00:00 EST 1993},
month = {Wed Jan 20 00:00:00 EST 1993}
}