Journal article

Publication year: 2003

Pages: 4313-4320

Journal: European Journal of Inorganic Chemistry

Issue number: 24

ISSN: 1434-1948

eISSN: 1099-0682

Open access status: Bronze

DOI Link: https://doi.org/10.1002/ejic.200300314

Publisher: Wiley-VCH Verlag

Abstract: 
The thermal isomerizations of eta(1)-vinylidene complexes [(Tl C5H5)(CO)(NO)W=C=CHR] 15a, R = Si(CH3)(2)C(CH3)(3); 5c, R C(CH3)(3)] as well as [(eta(5) -C5H5)(CO)(NO)Mo=C=CHC(CH3)(3)] (8), to the corresponding eta(2)-1-alkyne complexes [(eta(5)C(5)H(5))(CO)(NO)W(eta (2) -H-CdropC-R)] [7a, R = Si(CH3)(2)C(CH3)(3); 7c, R = C(CH3)(3)] and eta(5)-C5H5)(CO)(NO)Mo(eta(2)-H-CdropC-CHC(CH3)(3))] (9) has been investigated. Activation parameters for the isomerization of 5a in [D-6]benzene and 8 in [D-8]toluene and [D-5]ethanol were determined. In [D-8]toluene eta(1)-vinylidene complex 5a undergoes a single step 1,2-shift of the silyl group from C-beta to C-alpha. However, complex 8 shows dichotomous behavior. The isomerization 8 9, dependent upon the solvent applied, occurs by means of two different pathways: in a nonpolar solvent, 8 tautomerizes via the 1,2-migration of the hydrogen atom to 9 and in ethanol this tautomerization proceeds by a multi-step process via deprotonation-protonation and subsequent reductive elimination. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Harvard Citation style: Ipaktschi, J., Mohsseni-Ala, J. and Uhlig, S. (2003) η¹-vinylidene to η²-alkyne isomerization of tungsten and molybdenum complexes, European Journal of Inorganic Chemistry(24), pp. 4313-4320. https://doi.org/10.1002/ejic.200300314

APA Citation style: Ipaktschi, J., Mohsseni-Ala, J., & Uhlig, S. (2003). η¹-vinylidene to η²-alkyne isomerization of tungsten and molybdenum complexes. European Journal of Inorganic Chemistry(24), 4313-4320. https://doi.org/10.1002/ejic.200300314