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
Hauptverfasser: Boynton, Jessica N, Guo, Jing-Dong, Grandjean, Fernande, Fettinger, James C, Nagase, Shigeru, Long, Gary J, Power, Philip P
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container_end_page 14223
container_issue 24
container_start_page 14216
container_title Inorganic chemistry
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creator Boynton, Jessica N
Guo, Jing-Dong
Grandjean, Fernande
Fettinger, James C
Nagase, Shigeru
Long, Gary J
Power, Philip P
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.
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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). 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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.</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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