Data · dataset · 2026
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
Listed in ZivaHub and Deakin Research Online and DMU Figshare — shown once because both records carry DOI 10.1021/acs.organomet.6c00224.s001
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.
Description
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.
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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.
Links
Where it is published
- DOI doi.org/10.1021/acs.organomet.6c00224.s001 ↗
DOI / persistent id · from zivahub uct ac za
Catalogue records · 1
- OAI-PMH record api.figshare.com/v2/oai?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai%3Af… ↗
metadata API · from zivahub uct ac za
Topics
- From keywords
- Biochemistry and cell biology · Biochemistry and cell biology · Biochemistry and cell biology · Cancer · Cancer · Cancer · Chemistry · Chemistry · Chemistry · Earth & Environmental Science · Earth & Environmental Science · Earth & Environmental Science · Genetics · Genetics · Genetics · Immunology · Immunology · Immunology · Life Sciences · Life Sciences · Life Sciences · Medicine & Health · Medicine & Health · Medicine & Health
Provenance · 3 source records, 29 field assertions
| Source | Key | Last seen | Raw |
|---|---|---|---|
| ZivaHub | oai:figshare.com:article/34033401 | 10 d ago | JSON v1 |
| Deakin Research Online | oai:figshare.com:article/34033401 | 10 d ago | JSON v1 |
| DMU Figshare | oai:figshare.com:article/34033401 | 10 d ago | JSON v1 |
| Field | Assertion | Extractor | Evidence |
|---|---|---|---|
| access_level | source · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | |
| concepts[disease].local:disease:cancer | mapping · dro deakin edu au | vocabulary-mapper@1.0.0 | keywords['Cancer'] |
| concepts[disease].local:disease:cancer | mapping · zivahub uct ac za | vocabulary-mapper@1.0.0 | keywords['Cancer'] |
| concepts[disease].local:disease:cancer | mapping · figshare dmu ac uk | vocabulary-mapper@1.0.0 | keywords['Cancer'] |
| concepts[field].anzsrc:group:3101 | mapping · zivahub uct ac za | vocabulary-mapper@1.0.0 | keywords['Cell Biology'] |
| concepts[field].anzsrc:group:3101 | mapping · dro deakin edu au | vocabulary-mapper@1.0.0 | keywords['Cell Biology'] |
| concepts[field].anzsrc:group:3101 | mapping · figshare dmu ac uk | vocabulary-mapper@1.0.0 | keywords['Cell Biology'] |
| concepts[field].anzsrc:group:3105 | mapping · dro deakin edu au | vocabulary-mapper@1.0.0 | keywords['Genetics'] |
| concepts[field].anzsrc:group:3105 | mapping · figshare dmu ac uk | vocabulary-mapper@1.0.0 | keywords['Genetics'] |
| concepts[field].anzsrc:group:3105 | mapping · zivahub uct ac za | vocabulary-mapper@1.0.0 | keywords['Genetics'] |
| concepts[field].anzsrc:group:3204 | mapping · figshare dmu ac uk | vocabulary-mapper@1.0.0 | keywords['Immunology'] |
| concepts[field].anzsrc:group:3204 | mapping · zivahub uct ac za | vocabulary-mapper@1.0.0 | keywords['Immunology'] |
| concepts[field].anzsrc:group:3204 | mapping · dro deakin edu au | vocabulary-mapper@1.0.0 | keywords['Immunology'] |
| concepts[field].local:field:chemistry | mapping · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | |
| concepts[field].local:field:chemistry | mapping · figshare dmu ac uk | connector:figshare_dmu_ac_uk@1.0.0 | |
| concepts[field].local:field:chemistry | mapping · dro deakin edu au | connector:dro_deakin_edu_au@1.0.0 | |
| concepts[field].local:field:earth-environmental | mapping · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | |
| concepts[field].local:field:earth-environmental | mapping · dro deakin edu au | connector:dro_deakin_edu_au@1.0.0 | |
| concepts[field].local:field:earth-environmental | mapping · figshare dmu ac uk | connector:figshare_dmu_ac_uk@1.0.0 | |
| concepts[field].local:field:life-sciences | mapping · dro deakin edu au | connector:dro_deakin_edu_au@1.0.0 | |
| concepts[field].local:field:life-sciences | mapping · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | |
| concepts[field].local:field:life-sciences | mapping · figshare dmu ac uk | connector:figshare_dmu_ac_uk@1.0.0 | |
| concepts[field].local:field:medicine-health | mapping · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | |
| concepts[field].local:field:medicine-health | mapping · figshare dmu ac uk | connector:figshare_dmu_ac_uk@1.0.0 | |
| concepts[field].local:field:medicine-health | mapping · dro deakin edu au | connector:dro_deakin_edu_au@1.0.0 | |
| description | source · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | /metadata/dc/description |
| license | source · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | /metadata/dc/rights |
| publication_date | source · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | |
| title | source · zivahub uct ac za | connector:zivahub_uct_ac_za@1.0.0 | /metadata/dc/title |