Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster.
The electronic structure of so-called 'xenophilic' clusters, which contain both organometallic fragments and Werner-type paramagnetic transition metal centres, presents a challenge to simple theories of bonding. Density functional theory shows clearly that the cluster Mn(2)(thf)(4)(Fe(CO)(...
| Main Authors: | , , |
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| Format: | Journal article |
| Language: | English |
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2011
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| _version_ | 1826284877792673792 |
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| author | Krämer, T Lin, Z McGrady, J |
| author_facet | Krämer, T Lin, Z McGrady, J |
| author_sort | Krämer, T |
| collection | OXFORD |
| description | The electronic structure of so-called 'xenophilic' clusters, which contain both organometallic fragments and Werner-type paramagnetic transition metal centres, presents a challenge to simple theories of bonding. Density functional theory shows clearly that the cluster Mn(2)(thf)(4)(Fe(CO)(4))(2) is best described as an exchange-coupled Mn(II)(2) dimer, the closed-shell organometallic [Fe(CO)(4)](2-) fragments acting simply as bridging ligands. The high-spin configuration of the Mn(II) ions leads to single occupation of the Mn-Fe σ* orbitals and therefore substantially weaker metal-metal bonding than in conventional low-valent organometallic clusters. The transition metal fragments are effective mediators of superexchange (J(calc) = -44 cm(-1)), leading to the measured effective magnetic moment of ~5 μ(B) at 300 K, considerably lower than the limiting value of 8.37 μ(B) for two uncoupled S = 5/2 Mn(II) centres. |
| first_indexed | 2024-03-07T01:20:26Z |
| format | Journal article |
| id | oxford-uuid:901e90d4-5c55-4c78-ac8e-2fe11e4d6427 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:20:26Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | oxford-uuid:901e90d4-5c55-4c78-ac8e-2fe11e4d64272022-03-26T23:09:31ZExchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:901e90d4-5c55-4c78-ac8e-2fe11e4d6427EnglishSymplectic Elements at Oxford2011Krämer, TLin, ZMcGrady, JThe electronic structure of so-called 'xenophilic' clusters, which contain both organometallic fragments and Werner-type paramagnetic transition metal centres, presents a challenge to simple theories of bonding. Density functional theory shows clearly that the cluster Mn(2)(thf)(4)(Fe(CO)(4))(2) is best described as an exchange-coupled Mn(II)(2) dimer, the closed-shell organometallic [Fe(CO)(4)](2-) fragments acting simply as bridging ligands. The high-spin configuration of the Mn(II) ions leads to single occupation of the Mn-Fe σ* orbitals and therefore substantially weaker metal-metal bonding than in conventional low-valent organometallic clusters. The transition metal fragments are effective mediators of superexchange (J(calc) = -44 cm(-1)), leading to the measured effective magnetic moment of ~5 μ(B) at 300 K, considerably lower than the limiting value of 8.37 μ(B) for two uncoupled S = 5/2 Mn(II) centres. |
| spellingShingle | Krämer, T Lin, Z McGrady, J Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster. |
| title | Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster. |
| title_full | Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster. |
| title_fullStr | Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster. |
| title_full_unstemmed | Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster. |
| title_short | Exchange coupling through diamagnetic [Fe(CO)4]2- bridging ligands in a xenophilic cluster. |
| title_sort | exchange coupling through diamagnetic fe co 4 2 bridging ligands in a xenophilic cluster |
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