Synthesis and characterization of the titanium bisamide Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 and its TiCl{N(H)Ar(iPr6)}2 precursor: Ti(II) → Ti(IV) cyclization
The titanium bisamido complex Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 (2), along with its three-coordinate titanium(III) precursor, TiCl{N(H)Ar(iPr6)}2 (1), have been synthesized and characterized. Compound 1 was obtained via the stoichiometric reaction of LiN(H)Ar(iPr6) with the...
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Veröffentlicht in: | Inorganic chemistry 2013-12, Vol.52 (24), p.14216-14223 |
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description | The titanium bisamido complex Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 (2), along with its three-coordinate titanium(III) precursor, TiCl{N(H)Ar(iPr6)}2 (1), have been synthesized and characterized. Compound 1 was obtained via the stoichiometric reaction of LiN(H)Ar(iPr6) with the Ti(III) complex TiCl3·2NMe3 in trimethylamine. Reduction of 1 with 1 equiv of KC8 afforded Ti{N(H)Ar(iPr6)}2 (2) in moderate yield. Both 1 and 2 were characterized by X-ray crystallography, NMR, and IR spectroscopy, magnetic studies, and by density functional theory (DFT) computations. The precursor 1 has quasi-four-coordinate coordination at the titanium atom, with bonding to two amido nitrogens and a chlorine as well as a secondary interaction to a flanking aryl ring of a terphenyl substituent. Compound 2 displays a very distorted four-coordinate metal environment in which the titanium atom is bound to two amido nitrogens and to two carbons from a terphenyl aryl ring. This structure is in sharp contrast to the expected two-coordinate linear structure that was observed in its first row metal (V-Ni) analogues. Magnetic studies confirm a d(1) electron configuration for 1 but indicate that Ti{N(H)Ar(iPr6)}2 (2) is diamagnetic at ambient temperature consistent with the oxidation of titanium to Ti(IV). The different structure of 2 is attributed to the high reducing tendency of the Ti(II) in comparison to the other metals. |
doi_str_mv | 10.1021/ic4021355 |
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Compound 1 was obtained via the stoichiometric reaction of LiN(H)Ar(iPr6) with the Ti(III) complex TiCl3·2NMe3 in trimethylamine. Reduction of 1 with 1 equiv of KC8 afforded Ti{N(H)Ar(iPr6)}2 (2) in moderate yield. Both 1 and 2 were characterized by X-ray crystallography, NMR, and IR spectroscopy, magnetic studies, and by density functional theory (DFT) computations. The precursor 1 has quasi-four-coordinate coordination at the titanium atom, with bonding to two amido nitrogens and a chlorine as well as a secondary interaction to a flanking aryl ring of a terphenyl substituent. Compound 2 displays a very distorted four-coordinate metal environment in which the titanium atom is bound to two amido nitrogens and to two carbons from a terphenyl aryl ring. This structure is in sharp contrast to the expected two-coordinate linear structure that was observed in its first row metal (V-Ni) analogues. Magnetic studies confirm a d(1) electron configuration for 1 but indicate that Ti{N(H)Ar(iPr6)}2 (2) is diamagnetic at ambient temperature consistent with the oxidation of titanium to Ti(IV). The different structure of 2 is attributed to the high reducing tendency of the Ti(II) in comparison to the other metals.</description><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic4021355</identifier><identifier>PMID: 24266522</identifier><language>eng</language><publisher>United States</publisher><ispartof>Inorganic chemistry, 2013-12, Vol.52 (24), p.14216-14223</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,27929,27930</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24266522$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Boynton, Jessica N</creatorcontrib><creatorcontrib>Guo, Jing-Dong</creatorcontrib><creatorcontrib>Grandjean, Fernande</creatorcontrib><creatorcontrib>Fettinger, James C</creatorcontrib><creatorcontrib>Nagase, Shigeru</creatorcontrib><creatorcontrib>Long, Gary J</creatorcontrib><creatorcontrib>Power, Philip P</creatorcontrib><title>Synthesis and characterization of the titanium bisamide Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 and its TiCl{N(H)Ar(iPr6)}2 precursor: Ti(II) → Ti(IV) cyclization</title><title>Inorganic chemistry</title><addtitle>Inorg Chem</addtitle><description>The titanium bisamido complex Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 (2), along with its three-coordinate titanium(III) precursor, TiCl{N(H)Ar(iPr6)}2 (1), have been synthesized and characterized. Compound 1 was obtained via the stoichiometric reaction of LiN(H)Ar(iPr6) with the Ti(III) complex TiCl3·2NMe3 in trimethylamine. Reduction of 1 with 1 equiv of KC8 afforded Ti{N(H)Ar(iPr6)}2 (2) in moderate yield. Both 1 and 2 were characterized by X-ray crystallography, NMR, and IR spectroscopy, magnetic studies, and by density functional theory (DFT) computations. The precursor 1 has quasi-four-coordinate coordination at the titanium atom, with bonding to two amido nitrogens and a chlorine as well as a secondary interaction to a flanking aryl ring of a terphenyl substituent. Compound 2 displays a very distorted four-coordinate metal environment in which the titanium atom is bound to two amido nitrogens and to two carbons from a terphenyl aryl ring. This structure is in sharp contrast to the expected two-coordinate linear structure that was observed in its first row metal (V-Ni) analogues. Magnetic studies confirm a d(1) electron configuration for 1 but indicate that Ti{N(H)Ar(iPr6)}2 (2) is diamagnetic at ambient temperature consistent with the oxidation of titanium to Ti(IV). The different structure of 2 is attributed to the high reducing tendency of the Ti(II) in comparison to the other metals.</description><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNpdkMtKAzEYhYMgtlYXvoBkOQOOJplJphVclEFtoWjBIu6GTC40MpeazCyquPUBfBqfxycx1nbj6nxwDuf_OQCcYHSOEcEXRiReYkr3QB9TgiKK0VMPHDr3jBAaxQk7AD2SEMYoIX3w9bCu26VyxkFeSyiW3HLRKmteeWuaGjYaehu2puW16SpYGMcrIxVcmLe7YBKObWDmloXvBAY7hlcwY5M4ImcsCjwRT8kvm3Bu45BsLpnW-Y6s_N-yskp01jX20tvBdBrC74_PDT6GUKxFuf3sCOxrXjp1vNUBWNxcL7JJNLu_nWbjWbSijETJSFI01IJIIuJYaKxTiflQFqpIEWJM-km0okgyyZSkuFBCi6FOtUhTohMVD0DwV7uyzUunXJtXxglVlrxWTedynKQpZZQx7KOn22hXVErmK2sqbtf5buz4B982eoY</recordid><startdate>20131216</startdate><enddate>20131216</enddate><creator>Boynton, Jessica N</creator><creator>Guo, Jing-Dong</creator><creator>Grandjean, Fernande</creator><creator>Fettinger, James C</creator><creator>Nagase, Shigeru</creator><creator>Long, Gary J</creator><creator>Power, Philip P</creator><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20131216</creationdate><title>Synthesis and characterization of the titanium bisamide Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 and its TiCl{N(H)Ar(iPr6)}2 precursor: Ti(II) → Ti(IV) cyclization</title><author>Boynton, Jessica N ; Guo, Jing-Dong ; Grandjean, Fernande ; Fettinger, James C ; Nagase, Shigeru ; Long, Gary J ; Power, Philip P</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-p562-49d508fc2d2c33cf1f7d1a8dbeb70066d009fe50d6d6ed51becfc8f7fc772f4e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Boynton, Jessica N</creatorcontrib><creatorcontrib>Guo, Jing-Dong</creatorcontrib><creatorcontrib>Grandjean, Fernande</creatorcontrib><creatorcontrib>Fettinger, James C</creatorcontrib><creatorcontrib>Nagase, Shigeru</creatorcontrib><creatorcontrib>Long, Gary J</creatorcontrib><creatorcontrib>Power, Philip P</creatorcontrib><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Boynton, Jessica N</au><au>Guo, Jing-Dong</au><au>Grandjean, Fernande</au><au>Fettinger, James C</au><au>Nagase, Shigeru</au><au>Long, Gary J</au><au>Power, Philip P</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and characterization of the titanium bisamide Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 and its TiCl{N(H)Ar(iPr6)}2 precursor: Ti(II) → Ti(IV) cyclization</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg Chem</addtitle><date>2013-12-16</date><risdate>2013</risdate><volume>52</volume><issue>24</issue><spage>14216</spage><epage>14223</epage><pages>14216-14223</pages><eissn>1520-510X</eissn><abstract>The titanium bisamido complex Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 (2), along with its three-coordinate titanium(III) precursor, TiCl{N(H)Ar(iPr6)}2 (1), have been synthesized and characterized. Compound 1 was obtained via the stoichiometric reaction of LiN(H)Ar(iPr6) with the Ti(III) complex TiCl3·2NMe3 in trimethylamine. Reduction of 1 with 1 equiv of KC8 afforded Ti{N(H)Ar(iPr6)}2 (2) in moderate yield. Both 1 and 2 were characterized by X-ray crystallography, NMR, and IR spectroscopy, magnetic studies, and by density functional theory (DFT) computations. The precursor 1 has quasi-four-coordinate coordination at the titanium atom, with bonding to two amido nitrogens and a chlorine as well as a secondary interaction to a flanking aryl ring of a terphenyl substituent. Compound 2 displays a very distorted four-coordinate metal environment in which the titanium atom is bound to two amido nitrogens and to two carbons from a terphenyl aryl ring. This structure is in sharp contrast to the expected two-coordinate linear structure that was observed in its first row metal (V-Ni) analogues. Magnetic studies confirm a d(1) electron configuration for 1 but indicate that Ti{N(H)Ar(iPr6)}2 (2) is diamagnetic at ambient temperature consistent with the oxidation of titanium to Ti(IV). The different structure of 2 is attributed to the high reducing tendency of the Ti(II) in comparison to the other metals.</abstract><cop>United States</cop><pmid>24266522</pmid><doi>10.1021/ic4021355</doi><tpages>8</tpages></addata></record> |
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title | Synthesis and characterization of the titanium bisamide Ti{N(H)Ar(iPr6)}2 (Ar(iPr6) = C6H3-2,6-(C6H2-2,4,6-(i)Pr3)2 and its TiCl{N(H)Ar(iPr6)}2 precursor: Ti(II) → Ti(IV) cyclization |
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