Journal article

Publication year: 2003

Pages: 66-74

Journal: Journal of Organometallic Chemistry

Volume number: 670

Issue number: 1-2

ISSN: 0022-328X

DOI Link: https://doi.org/10.1016/S0022-328X(02)02132-0

Publisher: Elsevier

Abstract: 
Treatment of the eta(1)-acetylide complex [(eta5-C5H5)(CO)(NO)W-C--C-C(CH3)(3)]Li (4) with 1,2-diiodoethane in THF at -78 degreesC, followed by the addition of Li-CdropC-R [R = C(CH3)(3), C6H5, Si(CH3)(3), 6a-6c] or n-C4H9Li and protonation with H2O, afforded the corresponding oxametallacyclopentadienyl complexes (eta(5)-C5H5)W(I)(NO)[eta(2)-O=C(CdropC-R)CH=CC(CH3)(3)](7a-7c), 8c and (eta(5)-C5H5)W(I)(NO)[eta(2)-O=C(n-C4H9)CH=CC(CH3)(3)] (9). The formation of these metallafuran derivatives is rationalized by the electrophilic attack of 1,2-diiodoethane onto the metal center of 4 to form first the neutral complex [(eta(5)-C5H5)(I)(CO)(NO)W-Cdrop C-C(CH3)31(5). Subsequent nucleophilic addition of Li-C--C-R 6a-6c or n-C4H9Li and a reductive elimination step followed by protonation leads to the products 7a-7c and 9. One reaction intermediate could be trapped with CF3SO3CH3 and characterized by a crystal structure analysis. The identity of another intermediate was established by infrared spectroscopic data. The oxametallacyclopentadienyl complex 10 forms in the presence of excess 1,2-diiodoethane through an alternative pathway and crystallizes as a clathrate containing iodine. (C) 2002 Elsevier Science B.V. All rights reserved.

Harvard Citation style: Ipaktschi, J., Reimann, K., Serafin, M. and Dülmer, A. (2003) η¹-Alkynyl and vinylidene transition metal complexes 10.: Reaction of the metal-acetylide [(η⁵-C₅H₅)(CO)(NO)W-CC-C(CH₃)₃]Li with 1,2-diiodoethane as electrophile and with various nucleophiles, Journal of Organometallic Chemistry, 670(1-2), Article PII S0022-328X(02)02132-0. pp. 66-74. https://doi.org/10.1016/S0022-328X(02)02132-0

APA Citation style: Ipaktschi, J., Reimann, K., Serafin, M., & Dülmer, A. (2003). η¹-Alkynyl and vinylidene transition metal complexes 10.: Reaction of the metal-acetylide [(η⁵-C₅H₅)(CO)(NO)W-CC-C(CH₃)₃]Li with 1,2-diiodoethane as electrophile and with various nucleophiles. Journal of Organometallic Chemistry. 670(1-2), Article PII S0022-328X(02)02132-0, 66-74. https://doi.org/10.1016/S0022-328X(02)02132-0