Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand
One electron oxidation of the monometallic alkenylacetylide complexes [Ru{C≡CC(R)=CH<sub>2</sub>}(dppe)Cp*] (<b>1</b>) and [Ru{C≡CC(R)=CH<sub>2</sub>}Cl(dppe)<sub>2</sub>] (<b>2</b>) (R = Ph (<b>a</b>); R = 4-MeS-C<sub>6&l...
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| Format: | Article |
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MDPI AG
2024-01-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/12/1/20 |
| _version_ | 1797343444436254720 |
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| author | Michael R. Hall Stephen A. Moggach Paul J. Low |
| author_facet | Michael R. Hall Stephen A. Moggach Paul J. Low |
| author_sort | Michael R. Hall |
| collection | DOAJ |
| description | One electron oxidation of the monometallic alkenylacetylide complexes [Ru{C≡CC(R)=CH<sub>2</sub>}(dppe)Cp*] (<b>1</b>) and [Ru{C≡CC(R)=CH<sub>2</sub>}Cl(dppe)<sub>2</sub>] (<b>2</b>) (R = Ph (<b>a</b>); R = 4-MeS-C<sub>6</sub>H<sub>4</sub> (<b>b</b>)) generates in each case a dinuclear bis(allenylidene) complex [{Ru}<sub>2</sub>{μ-C=C=C(R)–CH<sub>2</sub>–H<sub>2</sub>C–(R)C=C=C}][PF<sub>6</sub>]<sub>2</sub> ({Ru} = Ru(dppe)Cp* ([<b>3a</b>,<b>b</b>][PF<sub>6</sub>]<sub>2</sub>); {Ru} = RuCl(dppe)<sub>2</sub> ([<b>4a</b>,<b>b</b>][PF<sub>6</sub>]<sub>2</sub>), containing an unsaturated ethane bridge between both allenylidene moieties. Deprotonation of this ethane bridge results in the formation of the previously reported octa-3,5-diene-1,7-diyndiyl-bridged bimetallic species [{Ru}<sub>2</sub>{μ-C≡CC(R)=CH–HC=(R)CC≡C}] ({Ru} = Ru(dppe)Cp* (<b>5a</b>,<b>b</b>); {Ru} = RuCl(dppe)<sub>2</sub> (<b>6a</b>,<b>b</b>). The isolation of these complexes illustrates a general synthetic route to these conjugated bimetallic species from monomeric alkenylacetylide precursors. Electrochemical and spectroelectrochemical investigations evince the ready formation of the representative redox series [<b>5a</b>]<i><sup>n+</sup></i>, and TD-DFT calculations performed on optimised structures featuring the simplified {Ru(dmpe)Cp} coordination sphere [{Ru(dmpe)Cp}<sub>2</sub>{μ-C≡CC(Ph)=HC–CH(Ph)CC≡C}]<i><sup>n</sup></i><sup>+</sup> ([<b>5a</b><sup>†</sup>]<i><sup>n</sup></i><sup>+</sup>) (<i>n</i> = 0, 1, 2) reveal significant delocalisation of the unpaired charge in the formally mixed-valent species (<i>n</i> = 1), consistent with Class III assignment within the Robin–Day classification scheme. |
| first_indexed | 2024-03-08T10:47:47Z |
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| language | English |
| last_indexed | 2024-03-08T10:47:47Z |
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| spelling | doaj.art-e8d6a93fd39145d79a174337bf1681fe2024-01-26T17:04:01ZengMDPI AGInorganics2304-67402024-01-011212010.3390/inorganics12010020Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging LigandMichael R. Hall0Stephen A. Moggach1Paul J. Low2School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley 6009, AustraliaSchool of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley 6009, AustraliaSchool of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley 6009, AustraliaOne electron oxidation of the monometallic alkenylacetylide complexes [Ru{C≡CC(R)=CH<sub>2</sub>}(dppe)Cp*] (<b>1</b>) and [Ru{C≡CC(R)=CH<sub>2</sub>}Cl(dppe)<sub>2</sub>] (<b>2</b>) (R = Ph (<b>a</b>); R = 4-MeS-C<sub>6</sub>H<sub>4</sub> (<b>b</b>)) generates in each case a dinuclear bis(allenylidene) complex [{Ru}<sub>2</sub>{μ-C=C=C(R)–CH<sub>2</sub>–H<sub>2</sub>C–(R)C=C=C}][PF<sub>6</sub>]<sub>2</sub> ({Ru} = Ru(dppe)Cp* ([<b>3a</b>,<b>b</b>][PF<sub>6</sub>]<sub>2</sub>); {Ru} = RuCl(dppe)<sub>2</sub> ([<b>4a</b>,<b>b</b>][PF<sub>6</sub>]<sub>2</sub>), containing an unsaturated ethane bridge between both allenylidene moieties. Deprotonation of this ethane bridge results in the formation of the previously reported octa-3,5-diene-1,7-diyndiyl-bridged bimetallic species [{Ru}<sub>2</sub>{μ-C≡CC(R)=CH–HC=(R)CC≡C}] ({Ru} = Ru(dppe)Cp* (<b>5a</b>,<b>b</b>); {Ru} = RuCl(dppe)<sub>2</sub> (<b>6a</b>,<b>b</b>). The isolation of these complexes illustrates a general synthetic route to these conjugated bimetallic species from monomeric alkenylacetylide precursors. Electrochemical and spectroelectrochemical investigations evince the ready formation of the representative redox series [<b>5a</b>]<i><sup>n+</sup></i>, and TD-DFT calculations performed on optimised structures featuring the simplified {Ru(dmpe)Cp} coordination sphere [{Ru(dmpe)Cp}<sub>2</sub>{μ-C≡CC(Ph)=HC–CH(Ph)CC≡C}]<i><sup>n</sup></i><sup>+</sup> ([<b>5a</b><sup>†</sup>]<i><sup>n</sup></i><sup>+</sup>) (<i>n</i> = 0, 1, 2) reveal significant delocalisation of the unpaired charge in the formally mixed-valent species (<i>n</i> = 1), consistent with Class III assignment within the Robin–Day classification scheme.https://www.mdpi.com/2304-6740/12/1/20organometallic complexescumuleneoxidative couplingcarbon-rich ligandmixed-valenceRobin–Day classification |
| spellingShingle | Michael R. Hall Stephen A. Moggach Paul J. Low Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand Inorganics organometallic complexes cumulene oxidative coupling carbon-rich ligand mixed-valence Robin–Day classification |
| title | Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand |
| title_full | Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand |
| title_fullStr | Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand |
| title_full_unstemmed | Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand |
| title_short | Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand |
| title_sort | probing the electronic structure of dinuclear carbon rich complexes containing an octa 3 5 diene 1 7 diyndiyl bridging ligand |
| topic | organometallic complexes cumulene oxidative coupling carbon-rich ligand mixed-valence Robin–Day classification |
| url | https://www.mdpi.com/2304-6740/12/1/20 |
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