Journalartikel

Jahr der Veröffentlichung: 2001

Seiten: 4840-4846

Zeitschrift: Organometallics

Bandnummer: 20

Heftnummer: 23

ISSN: 0276-7333

DOI Link: https://doi.org/10.1021/om010528s

Verlag: American Chemical Society

Abstract: 
Primary and secondary amines 2a-d have been found to react in THF at room temperature with the vinylidene complexes [W(=C=CHR)(eta (5)-C5H5)(CO)(NO)] (R = C(CH3)(3) (1), R = Si(CH3)C(CH3)(3) (4)), affording the aminocarbene derivatives [W{=C((NRR2)-R-1)CH2C(CH3)(3)}(eta (5)-C5H5)(CO)(NO)] and [W{=C((NRR2)-R-1)CH2Si(CH3)(2)C(CH3)(3)}(eta (5)-C5H5)(CO)(NO)] (R-1 = H, R-2 = n-C4H9 (3a, 5a); R-1 = H, R-2 = CH(CH3)(2) (3b, 5b); R-1 = H, R-2 = C(CH3)(3) (3c, 5c); R-1 = R-2 = (CH2)(4) (3d, 5d)). At short reaction time the nucleophilic addition of both primary and secondary amines to 1 occurs at the carbonyl carbon atom, leading stereoselectively to the thermodynamically less stable eta (2)-carbamoyl-(Z)-vinyl complexes [W{sigma-(Z)-CH=CHC(CH3)(3)}-{eta (2)-C(O)(NRR2)-R-1} (eta (5)-C5H5)(NO)] (R-1 = H, R-2 = n-C4H9 (6a); R-1 = H, R-2 = CH(CH3)(3) (6b); R-1 = H, R-2 = C(CH3)(3) (6c); R-1 = R-2 = (CH2)(4) (6d)). At higher amine concentration and prolonged reaction time 6a-d form the corresponding aminocarbene complexes 3a-d. The structure of 6b has been authenticated by a single-crystal X-ray diffraction analysis.

Harvard-Zitierstil: Ipaktschi, J., Uhlig, S. and Dülmer, A. (2001) η²-alkynyl and vinylidene transition metal complexes.: 7.: Hydroamination of neutral tungsten-vinylidene complexes, Organometallics, 20(23), pp. 4840-4846. https://doi.org/10.1021/om010528s

APA-Zitierstil: Ipaktschi, J., Uhlig, S., & Dülmer, A. (2001). η²-alkynyl and vinylidene transition metal complexes.: 7.: Hydroamination of neutral tungsten-vinylidene complexes. Organometallics. 20(23), 4840-4846. https://doi.org/10.1021/om010528s