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Issue 13, 1997
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Regioselective reactions of isothiocyanates with the titanocene vinylidene fragment [Ti([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(η-C5Me 5)2]. Crystal and molecular structure of [[upper bond 1 start]Ti{SC([double bond, length as m-dash]NC6H11)C[upper bond 1 end][double bond, length as m-dash]CH2}(η-C5Me5 )2]

Abstract

The titanocene vinylidene intermediate [Ti([double bond, length as m-dash]C[double bond, length as m-dash]CH 2 )(η-C 5 Me 5 ) 2 ] 1 formed by ethane or methane elimination from [[upper bond 1 start]Ti(CH 2 CH 2 C[upper bond 1 end][double bond, length as m-dash]CH 2 )(η-C 5 Me 5 ) 2 ] 2 or [Ti(CH[double bond, length as m-dash]CH 2 )Me(η-C 5 Me 5 ) 2 ] 3 respectively, reacted with isothiocyanates RNCS (R = C 6 H 11 a, Ph b or Bu t c) by a [2 + 2] cycloaddition, to give the titanathietane complexes [[upper bond 1 start]Ti{SC([double bond, length as m-dash]NR)C[upper bond 1 end][double bond, length as m-dash]CH 2 }( η-C 5 Me 5 ) 2 ]. The crystal structure of the R = C 6 H 11 complex has been determined. In all cases the regioisomer in which the sulfur atom is bonded to titanium is observed as the primary product. Upon heating in the presence of pyridine a rearrangement to the regioisomeric titanacyclobutane derivative [[upper bond 1 start]Ti{C([double bond, length as m-dash]NR)SC[upper bond 1 end][double bond, length as m-dash]CH 2 }( η-C 5 Me 5 ) 2 ] was observed. The regioselectivity of the formation of the complexes 5 and 7 is discussed on the basis of ab initio calculations at the Hartree–Fock level of theory, with an effective core potential basis set.

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Article information


J. Chem. Soc., Dalton Trans., 1997, 2249-2256
Article type
Paper

Regioselective reactions of isothiocyanates with the titanocene vinylidene fragment [Ti([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(η-C5Me 5)2]. Crystal and molecular structure of [[upper bond 1 start]Ti{SC([double bond, length as m-dash]NC6H11)C[upper bond 1 end] [double bond, length as m-dash]CH2}(η-C5Me5 )2]

R. Beckhaus, J. Sang, T. Wagner and U. Böhme, J. Chem. Soc., Dalton Trans., 1997, 2249
DOI: 10.1039/A701499F

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