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Title: Electrophile-induced cyclizations of chiral rhenium ethynyl and C[sub 2]Li complexes of the formula ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (C[triple bond]CX). Synthesis, structure, and reactivity of unusual 1,3-dimetalated cyclic C[sub 4]H[sub 3] and C[sub 4]H[sub 4] species

Abstract

Reactions of ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3])(C=CH) (1) or ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3])(C[triple bond]CL) (2) and ZnCl[sub 2] ([ge] 1.2 eqiv) give the meso dirhenium complex (SR,RS)-[([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (=C=CH=C(CH[sub 2])=)(Ph[sub 3]P)(ON)Re([eta][sup 5]-C[sup -5]Me[sub 5])] [sup +]([Zn[sub 2]Cl[sub 6]][sup 2])[sub [1/2]] (4). Samples contain up to 10% of the corresponding dl diastereomer (total yield 94-38%). Mechanisms involving adventitious water and initial electrophilic attack upon C[sub [beta]] of I are proposed. Accordingly, addition of 0.5 equiv of HBF[sub 4]-OEt[sub 2] to 1 (CH[sub 2]Cl[sub 2], 25[degree]C) gives the analogous dirhenium tetrafluroborate salt 5 (85%). However, addition of 1 to 2.0 equiv of HBF[sub 4]-OEt[sub 2] (THF, [minus]80[degree]C) gives the vinylidine complex [([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (=C=CH[sub 2])][sup +]BF[sub 4][sup -] (6; 86%). Reaction of 1 and 6 (CH[sub 2]Cl[sub 2], 25[degree]C) also gives 5 (94%). The crystal structure of 4 shows rhenium-carbon bonds of 2.00(1)-2.03(1) A, intermediate between single and double bonds and consistent with a delocalized structure based upon Re=C=CHC(CH[sub 2])=Re[sup +] resonance forms. NMR data establish 12.1-12.6 kcal/mol Re=C rotational barriers. 32 refs., 3 figs., 3 tabs.

Authors:
; ; ; ;  [1]
  1. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
OSTI Identifier:
6455790
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 14:2; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; LITHIUM COMPLEXES; CHEMICAL REACTIONS; INFRARED SPECTRA; NMR SPECTRA; SYNTHESIS; ORGANOMETALLIC COMPOUNDS; RHENIUM COMPLEXES; BOND ANGLE; BOND LENGTHS; CRYSTAL STRUCTURE; MOLECULAR STRUCTURE; NUMERICAL DATA; COMPLEXES; DATA; DIMENSIONS; INFORMATION; LENGTH; ORGANIC COMPOUNDS; SPECTRA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400102 - Chemical & Spectral Procedures

Citation Formats

Weng, W, Bartik, T, Johnson, M T, Arif, A M, and Gladysz, J A. Electrophile-induced cyclizations of chiral rhenium ethynyl and C[sub 2]Li complexes of the formula ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (C[triple bond]CX). Synthesis, structure, and reactivity of unusual 1,3-dimetalated cyclic C[sub 4]H[sub 3] and C[sub 4]H[sub 4] species. United States: N. p., 1995. Web. doi:10.1021/om00002a041.
Weng, W, Bartik, T, Johnson, M T, Arif, A M, & Gladysz, J A. Electrophile-induced cyclizations of chiral rhenium ethynyl and C[sub 2]Li complexes of the formula ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (C[triple bond]CX). Synthesis, structure, and reactivity of unusual 1,3-dimetalated cyclic C[sub 4]H[sub 3] and C[sub 4]H[sub 4] species. United States. https://doi.org/10.1021/om00002a041
Weng, W, Bartik, T, Johnson, M T, Arif, A M, and Gladysz, J A. 1995. "Electrophile-induced cyclizations of chiral rhenium ethynyl and C[sub 2]Li complexes of the formula ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (C[triple bond]CX). Synthesis, structure, and reactivity of unusual 1,3-dimetalated cyclic C[sub 4]H[sub 3] and C[sub 4]H[sub 4] species". United States. https://doi.org/10.1021/om00002a041.
@article{osti_6455790,
title = {Electrophile-induced cyclizations of chiral rhenium ethynyl and C[sub 2]Li complexes of the formula ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (C[triple bond]CX). Synthesis, structure, and reactivity of unusual 1,3-dimetalated cyclic C[sub 4]H[sub 3] and C[sub 4]H[sub 4] species},
author = {Weng, W and Bartik, T and Johnson, M T and Arif, A M and Gladysz, J A},
abstractNote = {Reactions of ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3])(C=CH) (1) or ([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3])(C[triple bond]CL) (2) and ZnCl[sub 2] ([ge] 1.2 eqiv) give the meso dirhenium complex (SR,RS)-[([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (=C=CH=C(CH[sub 2])=)(Ph[sub 3]P)(ON)Re([eta][sup 5]-C[sup -5]Me[sub 5])] [sup +]([Zn[sub 2]Cl[sub 6]][sup 2])[sub [1/2]] (4). Samples contain up to 10% of the corresponding dl diastereomer (total yield 94-38%). Mechanisms involving adventitious water and initial electrophilic attack upon C[sub [beta]] of I are proposed. Accordingly, addition of 0.5 equiv of HBF[sub 4]-OEt[sub 2] to 1 (CH[sub 2]Cl[sub 2], 25[degree]C) gives the analogous dirhenium tetrafluroborate salt 5 (85%). However, addition of 1 to 2.0 equiv of HBF[sub 4]-OEt[sub 2] (THF, [minus]80[degree]C) gives the vinylidine complex [([eta][sup 5]-C[sub 5]Me[sub 5])Re(NO)(PPh[sub 3]) (=C=CH[sub 2])][sup +]BF[sub 4][sup -] (6; 86%). Reaction of 1 and 6 (CH[sub 2]Cl[sub 2], 25[degree]C) also gives 5 (94%). The crystal structure of 4 shows rhenium-carbon bonds of 2.00(1)-2.03(1) A, intermediate between single and double bonds and consistent with a delocalized structure based upon Re=C=CHC(CH[sub 2])=Re[sup +] resonance forms. NMR data establish 12.1-12.6 kcal/mol Re=C rotational barriers. 32 refs., 3 figs., 3 tabs.},
doi = {10.1021/om00002a041},
url = {https://www.osti.gov/biblio/6455790}, journal = {Organometallics; (United States)},
issn = {0276-7333},
number = ,
volume = 14:2,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 1995},
month = {Wed Feb 01 00:00:00 EST 1995}
}