2026-10-13T19:31:26Z
https://api.figshare.com/v2/oai
oai:figshare.com:article/33965082
2026-09-22T13:16:17Z
category_915
category_7
category_12
category_13
category_14
category_16
category_19
category_21
category_24
category_873
category_61
category_64
category_132
category_134
category_135
portal_63
item_type_3
month_year_09_2026
Reactivity
of a Bis(alkynyl)-Vinylidene Osmium Complex:
Access to Carbynes, Vinyl Ester Derivatives, and C–C and C–N
Bond-Forming Reactions
Sheila G. Curto (25090098)
Joaquín
M. Granados (25090101)
Enrique Oñate (1359039)
Montserrat Oliván (1359027)
Physical Sciences not elsewhere classified
Medicine
Cell Biology
Genetics
Molecular Biology
Physiology
Pharmacology
Biotechnology
Evolutionary Biology
Chemical Sciences not elsewhere classified
Developmental Biology
Cancer
Infectious Diseases
Virology
Computational Biology
vinyl ester derivatives
deuterium labeling experiments
density functional theory
bu ){ κ
bu )( p
acetic acid leads
bu }(= c
c ≡ c
c – c
bu )< sub
5 </ b
β </ sub
2 </ b
2 </ sub
3 </ sub
c </
2 -<
tert </
thermodynamic control
subsequent protonation
selective synthesis
new route
disubstituted imidazo
>- oc
>- butylacetylene
(< b
Hexahydride OsH<sub>6</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>1</b>)
reacts with <i>tert</i>-butylacetylene
to yield bis(alkynyl)-vinylidene Os(C≡C<sup>t</sup>Bu)<sub>2</sub>(=C=CH<sup>t</sup>Bu)(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>2</b>). Subsequent protonation of <b>2</b> with
HOTf or Et<sub>3</sub>N·3HF affords the bis(alkynyl)-carbyne
derivatives [Os(C≡C<sup>t</sup>Bu)<sub>2</sub>(≡CCH<sub>2</sub><sup>t</sup>Bu)(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub>]OTf
(<b>3</b>) and OsF(C≡C<sup>t</sup>Bu)<sub>2</sub>(≡CCH<sub>2</sub><sup>t</sup>Bu)(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>4</b>), respectively. In contrast, treatment of <b>2</b> with acetic acid leads to the alkynyl-vinylidene-vinyl ester derivative
Os(C≡C<sup>t</sup>Bu){κ<sup>2</sup>-<i>O,C</i>-OC(CH<sub>3</sub>)OC=CH<sup>t</sup>Bu}(=C=CH<sup>t</sup>Bu)(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>5</b>). Density functional
theory (DFT) calculations, together with deuterium labeling experiments,
demonstrate that the protonation may occur either at the C<sub>β</sub> carbon of the vinylidene ligand or at the C<sub>β</sub> carbon
atom of one of the alkynyl groups, and that the formation of <b>5</b> is governed by thermodynamic control. The reaction of <b>2</b> with 2-aminopyridine provides a new route for the selective
synthesis of a 2,3-disubstituted imidazo[1,2-<i>a</i>]pyridine
derivative starting from <i>tert</i>-butylacetylene and
2-aminopyridine.
2026-09-22T00:00:00Z
Dataset
Dataset
10.1021/acs.organomet.6c00277.s001
https://figshare.com/articles/dataset/Reactivity_of_a_Bis_alkynyl_-Vinylidene_Osmium_Complex_Access_to_Carbynes_Vinyl_Ester_Derivatives_and_C_C_and_C_N_Bond-Forming_Reactions/33965082
CC BY-NC 4.0