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Reactions
of [Ru<sub>3</sub>(CO)<sub>10</sub>(μ-dppf)]
with Internal Alkynes: A Fine Balance between C–H and P–C
Oxidative-Addition to the Triruthenium Center
Md. Arshad
H. Chowdhury (25144638)
Shahin A. Begum (25144641)
Jagodish C. Sarker (22293374)
Md. Monir Hossain (7477967)
Subas Rajbangshi (21224094)
Vladimir N. Nesterov (1689214)
Graeme Hogarth (710167)
Shariff E. Kabir (710165)
Biophysics
Biochemistry
Cell Biology
Genetics
Environmental Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
Immunology
Cancer
ray diffraction studies
appended diphosphine ligand
metalated dppf ligand
dppf )( μ
coordinated dppf ligand
stabilized triruthenium clusters
four new clusters
isolated products vary
capping alkyne ligand
1 ′- bis
toward internal alkynes
h ){ μ
h )( μ
5 </ sub
2 </ sub
r )< sub
c – h
r </
internal alkynes
electron clusters
triruthenium center
related diphosphine
four carbonyls
dppf )]
activated alkynes
two equivalents
open 52
metalation results
major product
formed via
fine balance
ethyl groups
cyclopentadienyl rings
crystal x
allenyl cluster
alkyne substituent
The reactivity of
[Ru<sub>3</sub>(CO)<sub>10</sub>(μ-dppf)]
(<b>1</b>) [dppf = 1,1′-bis(diphenylphosphino)ferrocene]
toward internal alkynes, RCCR (<i>R</i> = Et, Ph,
CO<sub>2</sub>Me, CO<sub>2</sub>Et), has been explored. Isolated products
vary with the nature of the alkyne substituent and differ from those
generated with related diphosphine-stabilized triruthenium clusters.
In all products, one or two equivalents of alkyne are incorporated
and three or four carbonyls are lost. With hex-3-yne, the allenyl
cluster [Ru<sub>3</sub>(CO)<sub>7</sub>(μ-H)(μ-dppf)(μ<sub>3</sub>-η<sup>1</sup>:η<sup>2</sup>:η<sup>2</sup>-MeCHCCEt)] (<b>2</b>) results via aliphatic C–H
bond activation of one of the ethyl groups. With diphenylacetylene,
the major product is [Ru<sub>3</sub>(CO)<sub>6</sub>(μ-H){μ-Ph<sub>2</sub>P(C<sub>5</sub>H<sub>3</sub>)Fe(C<sub>5</sub>H<sub>4</sub>)PPh<sub>2</sub>}(μ<sub>3</sub>-η<sup>1</sup>:η<sup>1</sup>:η<sup>2</sup>-PhC<sub>2</sub>Ph)] (<b>3</b>)
which contains a capping alkyne ligand and a metalated dppf ligand,
formed via C–H activation of one of the cyclopentadienyl rings.
Metalation results in formation of a dative Fe–Ru bond. With
activated alkynes (RCO<sub>2</sub>)C<sub>2</sub>(CO<sub>2</sub>R)
(<i>R</i> = Me, Et), alkyne coupling occurs to afford the
open 52-electron clusters [Ru<sub>3</sub>(μ-CO)(CO)<sub>6</sub>(μ-PPh<sub>2</sub>){μ-η<sup>1</sup>:κ<sup>1</sup>-Ph<sub>2</sub>P(C<sub>5</sub>H<sub>4</sub>)Fe(C<sub>5</sub>H<sub>4</sub>)}{μ<sub>3</sub>-η<sup>1</sup>:η<sup>2</sup>:η<sup>2</sup>:κ<sup>1</sup>-C<sub>4</sub>(CO<sub>2</sub>R)<sub>4</sub>}] (<b>4–5</b>). The later contain
bridging phosphido (PPh<sub>2</sub>) and chelating Ph<sub>2</sub>PFe(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub> ligands, formed via a previously
unreported P–C bond cleavage of the coordinated dppf ligand.
All four new clusters have been characterized by single-crystal X-ray
diffraction studies. We discuss likely reaction pathways and why these
transformations differ so much as a function of the appended diphosphine
ligand.
2026-09-30T00:00:00Z
Text
Journal contribution
10.1021/acs.organomet.6c00224.s001
https://figshare.com/articles/journal_contribution/Reactions_of_Ru_sub_3_sub_CO_sub_10_sub_-dppf_with_Internal_Alkynes_A_Fine_Balance_between_C_H_and_P_C_Oxidative-Addition_to_the_Triruthenium_Center/34033401
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