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]
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[...
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| Veröffentlicht in: | Inorganic chemistry 1993-01, Vol.32:2 |
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| creator | Schaller, C.P. Wolczanski, P.T. |
| description | 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_str_mv | 10.1021/ic00054a005 |
| format | Article |
| fullrecord | <record><control><sourceid>osti</sourceid><recordid>TN_cdi_osti_scitechconnect_6769983</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>6769983</sourcerecordid><originalsourceid>FETCH-osti_scitechconnect_67699833</originalsourceid><addsrcrecordid>eNqVjM1KAzEUhYModPxZ9QUuruqiejPTiY5LxdJNu5kuhDKUTHpLIyUpk5sBfSyf0CC66Uo353xwPo4QQ4m3EnN5Zw0ilhOd4kRkssxxXEp8PRUZYmKpVDUQ5yG8Ja0qJioTn3PinXYEfYCW3Acl1IZtr9l6B73VwJ12wZJjWIV4AG6eYoIWiqa2i9lSj1YbH9s9QevdplnU9li7-e68eYSau2g4dgR-C6PD--8yp3_cXIqzrd4HuvrpC3E9fVk-z8Y-sF0HY5nMznjnyPBa3auqeiiKP0lf-3JmgQ</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><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]</title><source>American Chemical Society Journals</source><creator>Schaller, C.P. ; Wolczanski, P.T.</creator><creatorcontrib>Schaller, C.P. ; Wolczanski, P.T.</creatorcontrib><description>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.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic00054a005</identifier><language>eng</language><publisher>United States</publisher><subject>02 PETROLEUM ; 020400 -- Petroleum-- Processing ; 03 NATURAL GAS ; 030300 -- Natural Gas-- Drilling, Production, & Processing ; 10 SYNTHETIC FUELS ; 100200 -- Synthetic Fuels-- Production-- (1990-) ; ALKANES ; AROMATICS ; BENZENE ; CHEMICAL ACTIVATION ; CHEMICAL REACTIONS ; COHERENT SCATTERING ; DATA ; DIFFRACTION ; EXPERIMENTAL DATA ; HYDROCARBONS ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; 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 400201 -- Chemical & Physicochemical Properties ; X-RAY DIFFRACTION</subject><ispartof>Inorganic chemistry, 1993-01, Vol.32:2</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27901,27902</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/6769983$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Schaller, C.P.</creatorcontrib><creatorcontrib>Wolczanski, P.T.</creatorcontrib><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]</title><title>Inorganic chemistry</title><description>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.</description><subject>02 PETROLEUM</subject><subject>020400 -- Petroleum-- Processing</subject><subject>03 NATURAL GAS</subject><subject>030300 -- Natural Gas-- Drilling, Production, & Processing</subject><subject>10 SYNTHETIC FUELS</subject><subject>100200 -- Synthetic Fuels-- Production-- (1990-)</subject><subject>ALKANES</subject><subject>AROMATICS</subject><subject>BENZENE</subject><subject>CHEMICAL ACTIVATION</subject><subject>CHEMICAL REACTIONS</subject><subject>COHERENT SCATTERING</subject><subject>DATA</subject><subject>DIFFRACTION</subject><subject>EXPERIMENTAL DATA</subject><subject>HYDROCARBONS</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>LATTICE PARAMETERS</subject><subject>MAGNETIC RESONANCE</subject><subject>METHANE</subject><subject>NUCLEAR MAGNETIC RESONANCE</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANOMETALLIC COMPOUNDS</subject><subject>PHYSICAL PROPERTIES</subject><subject>REFRACTORY METAL COMPOUNDS</subject><subject>RESONANCE</subject><subject>SCATTERING</subject><subject>TANTALUM COMPOUNDS</subject><subject>THERMAL DEGRADATION</subject><subject>THERMODYNAMIC PROPERTIES</subject><subject>TRANSITION ELEMENT COMPOUNDS 400201 -- Chemical & Physicochemical Properties</subject><subject>X-RAY DIFFRACTION</subject><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1993</creationdate><recordtype>article</recordtype><recordid>eNqVjM1KAzEUhYModPxZ9QUuruqiejPTiY5LxdJNu5kuhDKUTHpLIyUpk5sBfSyf0CC66Uo353xwPo4QQ4m3EnN5Zw0ilhOd4kRkssxxXEp8PRUZYmKpVDUQ5yG8Ja0qJioTn3PinXYEfYCW3Acl1IZtr9l6B73VwJ12wZJjWIV4AG6eYoIWiqa2i9lSj1YbH9s9QevdplnU9li7-e68eYSau2g4dgR-C6PD--8yp3_cXIqzrd4HuvrpC3E9fVk-z8Y-sF0HY5nMznjnyPBa3auqeiiKP0lf-3JmgQ</recordid><startdate>19930120</startdate><enddate>19930120</enddate><creator>Schaller, C.P.</creator><creator>Wolczanski, P.T.</creator><scope>OTOTI</scope></search><sort><creationdate>19930120</creationdate><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]</title><author>Schaller, C.P. ; Wolczanski, P.T.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-osti_scitechconnect_67699833</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1993</creationdate><topic>02 PETROLEUM</topic><topic>020400 -- Petroleum-- Processing</topic><topic>03 NATURAL GAS</topic><topic>030300 -- Natural Gas-- Drilling, Production, & Processing</topic><topic>10 SYNTHETIC FUELS</topic><topic>100200 -- Synthetic Fuels-- Production-- (1990-)</topic><topic>ALKANES</topic><topic>AROMATICS</topic><topic>BENZENE</topic><topic>CHEMICAL ACTIVATION</topic><topic>CHEMICAL REACTIONS</topic><topic>COHERENT SCATTERING</topic><topic>DATA</topic><topic>DIFFRACTION</topic><topic>EXPERIMENTAL DATA</topic><topic>HYDROCARBONS</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>LATTICE PARAMETERS</topic><topic>MAGNETIC RESONANCE</topic><topic>METHANE</topic><topic>NUCLEAR MAGNETIC RESONANCE</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANOMETALLIC COMPOUNDS</topic><topic>PHYSICAL PROPERTIES</topic><topic>REFRACTORY METAL COMPOUNDS</topic><topic>RESONANCE</topic><topic>SCATTERING</topic><topic>TANTALUM COMPOUNDS</topic><topic>THERMAL DEGRADATION</topic><topic>THERMODYNAMIC PROPERTIES</topic><topic>TRANSITION ELEMENT COMPOUNDS 400201 -- Chemical & Physicochemical Properties</topic><topic>X-RAY DIFFRACTION</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Schaller, C.P.</creatorcontrib><creatorcontrib>Wolczanski, P.T.</creatorcontrib><collection>OSTI.GOV</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Schaller, C.P.</au><au>Wolczanski, P.T.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>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]</atitle><jtitle>Inorganic chemistry</jtitle><date>1993-01-20</date><risdate>1993</risdate><volume>32:2</volume><issn>0020-1669</issn><eissn>1520-510X</eissn><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 obtained only at 182.8 (4) [degrees]C.</abstract><cop>United States</cop><doi>10.1021/ic00054a005</doi></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0020-1669 |
| ispartof | Inorganic chemistry, 1993-01, Vol.32:2 |
| issn | 0020-1669 1520-510X |
| language | eng |
| recordid | cdi_osti_scitechconnect_6769983 |
| source | American Chemical Society Journals |
| subjects | 02 PETROLEUM 020400 -- Petroleum-- Processing 03 NATURAL GAS 030300 -- Natural Gas-- Drilling, Production, & Processing 10 SYNTHETIC FUELS 100200 -- Synthetic Fuels-- Production-- (1990-) ALKANES AROMATICS BENZENE CHEMICAL ACTIVATION CHEMICAL REACTIONS COHERENT SCATTERING DATA DIFFRACTION EXPERIMENTAL DATA HYDROCARBONS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY 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 400201 -- Chemical & Physicochemical Properties X-RAY DIFFRACTION |
| 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] |
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