Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes.
The group 10 bis(phosphine)metalla[1]ferrocenophanes, [{Fe(η(5)-C(5)H(4))(2)}M(Pn-Bu(3))(2)] [M = Ni (4a), Pd (4b), and Pt (4c)], have been prepared by the reaction of Li(2)[Fe(η(5)-C(5)H(4))(2)]·tmeda (5, tmeda = N,N,N',N'-tetramethylethylenediamine) with trans-[MCl(2)(Pn-Bu(3))(2)] [M =...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Journal article |
| Language: | English |
| Published: |
2010
|
| _version_ | 1797104863928123392 |
|---|---|
| author | Matas, I Whittell, G Partridge, B Holland, J Haddow, M Green, J Manners, I |
| author_facet | Matas, I Whittell, G Partridge, B Holland, J Haddow, M Green, J Manners, I |
| author_sort | Matas, I |
| collection | OXFORD |
| description | The group 10 bis(phosphine)metalla[1]ferrocenophanes, [{Fe(η(5)-C(5)H(4))(2)}M(Pn-Bu(3))(2)] [M = Ni (4a), Pd (4b), and Pt (4c)], have been prepared by the reaction of Li(2)[Fe(η(5)-C(5)H(4))(2)]·tmeda (5, tmeda = N,N,N',N'-tetramethylethylenediamine) with trans-[MCl(2)(Pn-Bu(3))(2)] [M = Ni (trans-6a) and Pd (trans-6b)] and cis-[PtCl(2)(Pn-Bu(3))(2)] (cis-6c), respectively. Single crystal X-ray diffraction revealed highly tilted, strained structures as characterized by α angles of 28.4° (4a), 24.5° (4b), and 25.2° (4c) and a distorted square planar environment for the group 10 metal center. UV/visible spectroscopy and cyclic voltammetry indicated that all three compounds had smaller HOMO-LUMO gaps and were more electron-rich in nature than ferrocene and other comparable [1]ferrocenophanes. DFT calculations suggested that these differences were principally due to the electron-releasing nature of the M(Pn-Bu(3))(2) metal-ligand fragments. Attempts to induce thermal or anionic ring-opening polymerization of 4a-c were unsuccessful and were complicated by, for example, competing ligand dissociation processes or unfavorable chain propagation. In contrast, these species all reacted rapidly with acids effecting clean extrusion of the bis(phosphine)metal fragment. Carbon monoxide inserted cleanly into one of the palladium-carbon bonds of 4b to afford the ring-expanded, acylated product [{Fe(η(5)-C(5)H(4))(η(5)-C(5)H(4))(CO)}Pd(Pn-Bu(3))(2)] (10). The nickel analogue 4a, however, afforded [Ni(CO)(2)(Pn-Bu(3))(2)] whereas the platinum-bridged complex 4c was inert. Remarkably, all compounds 4a-c were readily oxidized by elemental sulfur to afford the [5,5']bicyclopentadienylidene (pentafulvalene) complexes [{η(4):η(0)-C(5)H(4)(C(5)H(4))}M(Pn-Bu(3))(2)] [M = Ni (11a)] and [(η(2)-C(10)H(8))M(Pn-Bu(3))(2)] [M = Pd (11b) and Pt (11c)] by a formal 4-electron oxidation of the carbocyclic ligands. Compounds 11b and 11c represent the first examples of [5,5']bicyclopentadienylidene as a neutral η(2)-ligand. The relative energies of η(2)-coordination with respect to that of η(4):η(0) bonding were investigated for 11a-c by DFT calculations. |
| first_indexed | 2024-03-07T06:39:33Z |
| format | Journal article |
| id | oxford-uuid:f8c9cc26-89f4-4a28-a1c6-1e36d0269194 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:39:33Z |
| publishDate | 2010 |
| record_format | dspace |
| spelling | oxford-uuid:f8c9cc26-89f4-4a28-a1c6-1e36d02691942022-03-27T12:53:09ZSynthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:f8c9cc26-89f4-4a28-a1c6-1e36d0269194EnglishSymplectic Elements at Oxford2010Matas, IWhittell, GPartridge, BHolland, JHaddow, MGreen, JManners, IThe group 10 bis(phosphine)metalla[1]ferrocenophanes, [{Fe(η(5)-C(5)H(4))(2)}M(Pn-Bu(3))(2)] [M = Ni (4a), Pd (4b), and Pt (4c)], have been prepared by the reaction of Li(2)[Fe(η(5)-C(5)H(4))(2)]·tmeda (5, tmeda = N,N,N',N'-tetramethylethylenediamine) with trans-[MCl(2)(Pn-Bu(3))(2)] [M = Ni (trans-6a) and Pd (trans-6b)] and cis-[PtCl(2)(Pn-Bu(3))(2)] (cis-6c), respectively. Single crystal X-ray diffraction revealed highly tilted, strained structures as characterized by α angles of 28.4° (4a), 24.5° (4b), and 25.2° (4c) and a distorted square planar environment for the group 10 metal center. UV/visible spectroscopy and cyclic voltammetry indicated that all three compounds had smaller HOMO-LUMO gaps and were more electron-rich in nature than ferrocene and other comparable [1]ferrocenophanes. DFT calculations suggested that these differences were principally due to the electron-releasing nature of the M(Pn-Bu(3))(2) metal-ligand fragments. Attempts to induce thermal or anionic ring-opening polymerization of 4a-c were unsuccessful and were complicated by, for example, competing ligand dissociation processes or unfavorable chain propagation. In contrast, these species all reacted rapidly with acids effecting clean extrusion of the bis(phosphine)metal fragment. Carbon monoxide inserted cleanly into one of the palladium-carbon bonds of 4b to afford the ring-expanded, acylated product [{Fe(η(5)-C(5)H(4))(η(5)-C(5)H(4))(CO)}Pd(Pn-Bu(3))(2)] (10). The nickel analogue 4a, however, afforded [Ni(CO)(2)(Pn-Bu(3))(2)] whereas the platinum-bridged complex 4c was inert. Remarkably, all compounds 4a-c were readily oxidized by elemental sulfur to afford the [5,5']bicyclopentadienylidene (pentafulvalene) complexes [{η(4):η(0)-C(5)H(4)(C(5)H(4))}M(Pn-Bu(3))(2)] [M = Ni (11a)] and [(η(2)-C(10)H(8))M(Pn-Bu(3))(2)] [M = Pd (11b) and Pt (11c)] by a formal 4-electron oxidation of the carbocyclic ligands. Compounds 11b and 11c represent the first examples of [5,5']bicyclopentadienylidene as a neutral η(2)-ligand. The relative energies of η(2)-coordination with respect to that of η(4):η(0) bonding were investigated for 11a-c by DFT calculations. |
| spellingShingle | Matas, I Whittell, G Partridge, B Holland, J Haddow, M Green, J Manners, I Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes. |
| title | Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes. |
| title_full | Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes. |
| title_fullStr | Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes. |
| title_full_unstemmed | Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes. |
| title_short | Synthesis, electronic structure, and reactivity of strained nickel-, palladium-, and platinum-bridged [1]ferrocenophanes. |
| title_sort | synthesis electronic structure and reactivity of strained nickel palladium and platinum bridged 1 ferrocenophanes |
| work_keys_str_mv | AT matasi synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes AT whittellg synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes AT partridgeb synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes AT hollandj synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes AT haddowm synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes AT greenj synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes AT mannersi synthesiselectronicstructureandreactivityofstrainednickelpalladiumandplatinumbridged1ferrocenophanes |