C−N Coupling Reactions of Allenes and Methylacetylenes with an Imidotitanium Complex

C−N Coupling Reactions of Allenes and Methylacetylenes with an Imidotitanium Complex

Reaction of the imidotitanium complexes [(N2Npy-κ3 N)Ti(NtBu)(py)] (1) and [(N2Npy-κ3 N)Ti(NtBu)] (1a) (N2Npy = (2-C5H4N)C(Me)(CH2NSiMe3)2) with 2-butyne and 1-phenylpropyne led to C−N coupling with the imido ligand and yielded the four-membered titanaazetidines [(N2Npy-κ3 N)Ti{N(tBu)C(CHCH3)CH2}]...

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Veröffentlicht in:Organometallics 2001-07, Vol.20 (15), p.3308-3313
Hauptverfasser: Trösch, Dominique J. M, Collier, Philip E, Bashall, Alan, Gade, Lutz H, McPartlin, Mary, Mountford, Philip, Radojevic, Sanja
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container_end_page 3313
container_issue 15
container_start_page 3308
container_title Organometallics
container_volume 20
creator Trösch, Dominique J. M
Collier, Philip E
Bashall, Alan
Gade, Lutz H
McPartlin, Mary
Mountford, Philip
Radojevic, Sanja
description Reaction of the imidotitanium complexes [(N2Npy-κ3 N)Ti(NtBu)(py)] (1) and [(N2Npy-κ3 N)Ti(NtBu)] (1a) (N2Npy = (2-C5H4N)C(Me)(CH2NSiMe3)2) with 2-butyne and 1-phenylpropyne led to C−N coupling with the imido ligand and yielded the four-membered titanaazetidines [(N2Npy-κ3 N)Ti{N(tBu)C(CHCH3)CH2}] (2) and [(N2Npy-κ3 N)Ti{N(tBu)C(CHC6H5)CH2}] (3), respectively. The same reaction products were obtained in 2 + 2 cycloaddition reactions of 1 and 1a with 1,2-butadiene and phenylallene. The four-membered metallacycle with an exocyclic CC double bond was established by X-ray diffraction studies of both compounds. A mechanism to explain the observed products from both types of reactions is proposed. Whereas the reactions of 1 with CO2, tBuNCO, and PhNCO were highly unspecific and did not lead to an isolable product, the conversion with the sterically encumbered isocyanate 2,6-iPr2C6H3NCO yielded the product of 2 + 2 cycloaddition to the TiN bond, namely [(N2Npy-κ3 N)Ti{N(tBu)C(N-2,6-C6H3 iPr2)O}(py)] (4), the structure of which was elucidated by NMR spectroscopy.
doi_str_mv 10.1021/om010253g
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M ; Collier, Philip E ; Bashall, Alan ; Gade, Lutz H ; McPartlin, Mary ; Mountford, Philip ; Radojevic, Sanja</creator><creatorcontrib>Trösch, Dominique J. M ; Collier, Philip E ; Bashall, Alan ; Gade, Lutz H ; McPartlin, Mary ; Mountford, Philip ; Radojevic, Sanja</creatorcontrib><description>Reaction of the imidotitanium complexes [(N2Npy-κ3 N)Ti(NtBu)(py)] (1) and [(N2Npy-κ3 N)Ti(NtBu)] (1a) (N2Npy = (2-C5H4N)C(Me)(CH2NSiMe3)2) with 2-butyne and 1-phenylpropyne led to C−N coupling with the imido ligand and yielded the four-membered titanaazetidines [(N2Npy-κ3 N)Ti{N(tBu)C(CHCH3)CH2}] (2) and [(N2Npy-κ3 N)Ti{N(tBu)C(CHC6H5)CH2}] (3), respectively. The same reaction products were obtained in 2 + 2 cycloaddition reactions of 1 and 1a with 1,2-butadiene and phenylallene. The four-membered metallacycle with an exocyclic CC double bond was established by X-ray diffraction studies of both compounds. A mechanism to explain the observed products from both types of reactions is proposed. Whereas the reactions of 1 with CO2, tBuNCO, and PhNCO were highly unspecific and did not lead to an isolable product, the conversion with the sterically encumbered isocyanate 2,6-iPr2C6H3NCO yielded the product of 2 + 2 cycloaddition to the TiN bond, namely [(N2Npy-κ3 N)Ti{N(tBu)C(N-2,6-C6H3 iPr2)O}(py)] (4), the structure of which was elucidated by NMR spectroscopy.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om010253g</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Organometallics, 2001-07, Vol.20 (15), p.3308-3313</ispartof><rights>Copyright © 2001 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a295t-b252c1d671a621c1895ea633f4b35cfcf1913e0cb43c40690b3f79273e351a5b3</citedby><cites>FETCH-LOGICAL-a295t-b252c1d671a621c1895ea633f4b35cfcf1913e0cb43c40690b3f79273e351a5b3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/om010253g$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/om010253g$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids></links><search><creatorcontrib>Trösch, Dominique J. 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M</creatorcontrib><creatorcontrib>Collier, Philip E</creatorcontrib><creatorcontrib>Bashall, Alan</creatorcontrib><creatorcontrib>Gade, Lutz H</creatorcontrib><creatorcontrib>McPartlin, Mary</creatorcontrib><creatorcontrib>Mountford, Philip</creatorcontrib><creatorcontrib>Radojevic, Sanja</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Trösch, Dominique J. M</au><au>Collier, Philip E</au><au>Bashall, Alan</au><au>Gade, Lutz H</au><au>McPartlin, Mary</au><au>Mountford, Philip</au><au>Radojevic, Sanja</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>C−N Coupling Reactions of Allenes and Methylacetylenes with an Imidotitanium Complex</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2001-07-23</date><risdate>2001</risdate><volume>20</volume><issue>15</issue><spage>3308</spage><epage>3313</epage><pages>3308-3313</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>Reaction of the imidotitanium complexes [(N2Npy-κ3 N)Ti(NtBu)(py)] (1) and [(N2Npy-κ3 N)Ti(NtBu)] (1a) (N2Npy = (2-C5H4N)C(Me)(CH2NSiMe3)2) with 2-butyne and 1-phenylpropyne led to C−N coupling with the imido ligand and yielded the four-membered titanaazetidines [(N2Npy-κ3 N)Ti{N(tBu)C(CHCH3)CH2}] (2) and [(N2Npy-κ3 N)Ti{N(tBu)C(CHC6H5)CH2}] (3), respectively. The same reaction products were obtained in 2 + 2 cycloaddition reactions of 1 and 1a with 1,2-butadiene and phenylallene. The four-membered metallacycle with an exocyclic CC double bond was established by X-ray diffraction studies of both compounds. A mechanism to explain the observed products from both types of reactions is proposed. Whereas the reactions of 1 with CO2, tBuNCO, and PhNCO were highly unspecific and did not lead to an isolable product, the conversion with the sterically encumbered isocyanate 2,6-iPr2C6H3NCO yielded the product of 2 + 2 cycloaddition to the TiN bond, namely [(N2Npy-κ3 N)Ti{N(tBu)C(N-2,6-C6H3 iPr2)O}(py)] (4), the structure of which was elucidated by NMR spectroscopy.</abstract><pub>American Chemical Society</pub><doi>10.1021/om010253g</doi><tpages>6</tpages></addata></record>
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