Dehydrogenation of hydrocarbons with metal-carbon multiple bonds and trapping of a titanium(II) intermediate

Reacting (PNP)Ti[double bond, length as m-dash]CH(t)Bu(CH2(t)Bu) with 2,2'-bipyridine (bipy) in cyclohexane or heptane results in dehydrogenation, cleanly producing cyclohexene and 1-heptene, respectively, and a Ti(II) intermediate that is trapped by bipy to produce [(PNP)Ti(III)(CH2(t)Bu)(bipy...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 43; no. 26; pp. 9834 - 9837
Main Authors Hickey, Anne K, Crestani, Marco G, Fout, Alison R, Gao, Xinfeng, Chen, Chun-Hsing, Mindiola, Daniel J
Format Journal Article
LanguageEnglish
Published England 14.07.2014
Subjects
Cleaning
Cyclohexane
Dehydrogenation
Diffraction
Hydrocarbons
Joining
Ligands
X-rays
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Summary:Reacting (PNP)Ti[double bond, length as m-dash]CH(t)Bu(CH2(t)Bu) with 2,2'-bipyridine (bipy) in cyclohexane or heptane results in dehydrogenation, cleanly producing cyclohexene and 1-heptene, respectively, and a Ti(II) intermediate that is trapped by bipy to produce [(PNP)Ti(III)(CH2(t)Bu)(bipy˙(-))] (1). This titanium(ii) intermediate reduces the bipy ligand upon coordination to form a Ti(III) center, where the unpaired electron is antiferromagnetically coupled to the electron of the reduced [bipy˙(-)] π-radical moiety, giving an overall diamagnetic species. Complex 1 has been characterized by NMR and UV-vis spectroscopies as well as single crystal X-ray diffraction studies.
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ISSN:1477-9226
1477-9234
DOI:10.1039/c4dt01037j