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Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms...
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| Zeitschriftentitel: | International Journal of Quantum Chemistry |
|---|---|
| Personen und Körperschaften: | , , , , , , , |
| In: | International Journal of Quantum Chemistry, 119, 2019, 22 |
| Format: | E-Article |
| Sprache: | Englisch |
| veröffentlicht: |
Wiley
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| Schlagwörter: |
| author_facet |
Wan, Di Li, Huidong Shi, Liming Wu, Xueke Fan, Qunchao Feng, Hao King, Robert Bruce Schaefer, Henry F. Wan, Di Li, Huidong Shi, Liming Wu, Xueke Fan, Qunchao Feng, Hao King, Robert Bruce Schaefer, Henry F. |
|---|---|
| author |
Wan, Di Li, Huidong Shi, Liming Wu, Xueke Fan, Qunchao Feng, Hao King, Robert Bruce Schaefer, Henry F. |
| spellingShingle |
Wan, Di Li, Huidong Shi, Liming Wu, Xueke Fan, Qunchao Feng, Hao King, Robert Bruce Schaefer, Henry F. International Journal of Quantum Chemistry Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms Physical and Theoretical Chemistry Condensed Matter Physics Atomic and Molecular Physics, and Optics |
| author_sort |
wan, di |
| spelling |
Wan, Di Li, Huidong Shi, Liming Wu, Xueke Fan, Qunchao Feng, Hao King, Robert Bruce Schaefer, Henry F. 0020-7608 1097-461X Wiley Physical and Theoretical Chemistry Condensed Matter Physics Atomic and Molecular Physics, and Optics http://dx.doi.org/10.1002/qua.26010 <jats:title>Abstract</jats:title><jats:p>The experimentally known split (3 + 2) five‐electron donor bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl (bcod) ligand provides a flexible alternative to the rigid planar cyclopentadienyl (Cp) ligand. In this connection, the structures and energetics of the binuclear iron carbonyl complexes (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 4, 3, 2, 1) have been investigated by density functional theory for comparison with the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> derivatives. The <jats:italic>cis</jats:italic> and <jats:italic>trans</jats:italic> doubly CO‐bridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(μ‐CO)<jats:sub>2</jats:sub>(CO)<jats:sub>2</jats:sub> structures are the lowest energy tetracarbonyl structures, similar to the Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> system. However, an unbridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> isomer lies only ~1 kcal/mol in energy above the doubly bridged isomers. The flexibility of the bcod ligand leads to low‐energy singlet and triplet spin state structures with agostic hydrogen atoms for the unsaturated (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 3, 2, 1) systems. Analogous structures are not found in the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> systems with the rigid Cp ligand. Such structures, effectively involving donation of an electron pair from an olefinic C‐H bond to an iron atom through three‐center two‐electron C‐H‐Fe bonding, are energetically competitive with isomeric structures with metal‐metal multiple bonds.</jats:p> Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms International Journal of Quantum Chemistry |
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10.1002/qua.26010 |
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Chemie und Pharmazie Physik |
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Wiley, 2019 |
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Wiley, 2019 |
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1097-461X 0020-7608 |
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| title |
Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_unstemmed |
Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_full |
Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_fullStr |
Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_full_unstemmed |
Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_short |
Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_sort |
unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: role of agostic hydrogen atoms |
| topic |
Physical and Theoretical Chemistry Condensed Matter Physics Atomic and Molecular Physics, and Optics |
| url |
http://dx.doi.org/10.1002/qua.26010 |
| publishDate |
2019 |
| physical |
|
| description |
<jats:title>Abstract</jats:title><jats:p>The experimentally known split (3 + 2) five‐electron donor bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl (bcod) ligand provides a flexible alternative to the rigid planar cyclopentadienyl (Cp) ligand. In this connection, the structures and energetics of the binuclear iron carbonyl complexes (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 4, 3, 2, 1) have been investigated by density functional theory for comparison with the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> derivatives. The <jats:italic>cis</jats:italic> and <jats:italic>trans</jats:italic> doubly CO‐bridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(μ‐CO)<jats:sub>2</jats:sub>(CO)<jats:sub>2</jats:sub> structures are the lowest energy tetracarbonyl structures, similar to the Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> system. However, an unbridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> isomer lies only ~1 kcal/mol in energy above the doubly bridged isomers. The flexibility of the bcod ligand leads to low‐energy singlet and triplet spin state structures with agostic hydrogen atoms for the unsaturated (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 3, 2, 1) systems. Analogous structures are not found in the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> systems with the rigid Cp ligand. Such structures, effectively involving donation of an electron pair from an olefinic C‐H bond to an iron atom through three‐center two‐electron C‐H‐Fe bonding, are energetically competitive with isomeric structures with metal‐metal multiple bonds.</jats:p> |
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| author | Wan, Di, Li, Huidong, Shi, Liming, Wu, Xueke, Fan, Qunchao, Feng, Hao, King, Robert Bruce, Schaefer, Henry F. |
| author_facet | Wan, Di, Li, Huidong, Shi, Liming, Wu, Xueke, Fan, Qunchao, Feng, Hao, King, Robert Bruce, Schaefer, Henry F., Wan, Di, Li, Huidong, Shi, Liming, Wu, Xueke, Fan, Qunchao, Feng, Hao, King, Robert Bruce, Schaefer, Henry F. |
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| description | <jats:title>Abstract</jats:title><jats:p>The experimentally known split (3 + 2) five‐electron donor bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl (bcod) ligand provides a flexible alternative to the rigid planar cyclopentadienyl (Cp) ligand. In this connection, the structures and energetics of the binuclear iron carbonyl complexes (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 4, 3, 2, 1) have been investigated by density functional theory for comparison with the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> derivatives. The <jats:italic>cis</jats:italic> and <jats:italic>trans</jats:italic> doubly CO‐bridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(μ‐CO)<jats:sub>2</jats:sub>(CO)<jats:sub>2</jats:sub> structures are the lowest energy tetracarbonyl structures, similar to the Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> system. However, an unbridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> isomer lies only ~1 kcal/mol in energy above the doubly bridged isomers. The flexibility of the bcod ligand leads to low‐energy singlet and triplet spin state structures with agostic hydrogen atoms for the unsaturated (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 3, 2, 1) systems. Analogous structures are not found in the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> systems with the rigid Cp ligand. Such structures, effectively involving donation of an electron pair from an olefinic C‐H bond to an iron atom through three‐center two‐electron C‐H‐Fe bonding, are energetically competitive with isomeric structures with metal‐metal multiple bonds.</jats:p> |
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| spelling | Wan, Di Li, Huidong Shi, Liming Wu, Xueke Fan, Qunchao Feng, Hao King, Robert Bruce Schaefer, Henry F. 0020-7608 1097-461X Wiley Physical and Theoretical Chemistry Condensed Matter Physics Atomic and Molecular Physics, and Optics http://dx.doi.org/10.1002/qua.26010 <jats:title>Abstract</jats:title><jats:p>The experimentally known split (3 + 2) five‐electron donor bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl (bcod) ligand provides a flexible alternative to the rigid planar cyclopentadienyl (Cp) ligand. In this connection, the structures and energetics of the binuclear iron carbonyl complexes (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 4, 3, 2, 1) have been investigated by density functional theory for comparison with the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> derivatives. The <jats:italic>cis</jats:italic> and <jats:italic>trans</jats:italic> doubly CO‐bridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(μ‐CO)<jats:sub>2</jats:sub>(CO)<jats:sub>2</jats:sub> structures are the lowest energy tetracarbonyl structures, similar to the Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> system. However, an unbridged (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> isomer lies only ~1 kcal/mol in energy above the doubly bridged isomers. The flexibility of the bcod ligand leads to low‐energy singlet and triplet spin state structures with agostic hydrogen atoms for the unsaturated (bcod)<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> (n = 3, 2, 1) systems. Analogous structures are not found in the corresponding Cp<jats:sub>2</jats:sub>Fe<jats:sub>2</jats:sub>(CO)<jats:sub>n</jats:sub> systems with the rigid Cp ligand. Such structures, effectively involving donation of an electron pair from an olefinic C‐H bond to an iron atom through three‐center two‐electron C‐H‐Fe bonding, are energetically competitive with isomeric structures with metal‐metal multiple bonds.</jats:p> Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms International Journal of Quantum Chemistry |
| spellingShingle | Wan, Di, Li, Huidong, Shi, Liming, Wu, Xueke, Fan, Qunchao, Feng, Hao, King, Robert Bruce, Schaefer, Henry F., International Journal of Quantum Chemistry, Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms, Physical and Theoretical Chemistry, Condensed Matter Physics, Atomic and Molecular Physics, and Optics |
| title | Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_full | Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_fullStr | Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_full_unstemmed | Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_short | Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| title_sort | unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: role of agostic hydrogen atoms |
| title_unstemmed | Unsaturation in binuclear iron carbonyl complexes of the split (3 + 2) five‐electron donor hydrocarbon ligand bicyclo[3.2.1]octa‐2,6‐dien‐4‐yl: Role of agostic hydrogen atoms |
| topic | Physical and Theoretical Chemistry, Condensed Matter Physics, Atomic and Molecular Physics, and Optics |
| url | http://dx.doi.org/10.1002/qua.26010 |