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Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η3-allyl) Complexes
Inorganic Chemistry, Volume: 54, Issue: 12, Pages: 5915 - 5929
Swansea University Author:
Russell Wakeham
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DOI (Published version): 10.1021/acs.inorgchem.5b00747
Abstract
Sequential treatment at low temperatures of Cp*W(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new Cp*W(NO)(H)(η3-allyl) complexes, namely, Cp*W(NO)(H)(η3-CH2CHCMe2) (1), Cp*W(NO)(H)(η3-CH2CHCHPh) (2), and Cp*W(NO)(H)(η3-CH2CHCHMe) (3)....
| Published in: | Inorganic Chemistry |
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| ISSN: | 0020-1669 1520-510X |
| Published: |
American Chemical Society (ACS)
2015
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| Online Access: |
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| URI: | https://cronfa.swan.ac.uk/Record/cronfa32710 |
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| Abstract: |
Sequential treatment at low temperatures of Cp*W(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new Cp*W(NO)(H)(η3-allyl) complexes, namely, Cp*W(NO)(H)(η3-CH2CHCMe2) (1), Cp*W(NO)(H)(η3-CH2CHCHPh) (2), and Cp*W(NO)(H)(η3-CH2CHCHMe) (3). Complexes 1–3 are isolable as air-stable, analytically pure yellow solids in good to moderate yields by chromatography or fractional crystallization. In solutions, complex 1 exists as two coordination isomers in an 83:17 ratio differing with respect to the endo/exo orientation of the allyl ligand. In contrast, complexes 2 and 3 each exist as four coordination isomers, all differing by the orientation of their allyl ligands which can have either an endo or an exo orientation with the phenyl or methyl groups being either proximal or distal to the nitrosyl ligand. A DFT computational analysis using the major isomer of Cp*W(NO)(H)(η3-CH2CHCHMe) (3a) as the model complex has revealed that its lowest-energy thermal-decomposition pathway involves the intramolecular isomerization of 3a to the 16e η2-alkene complex, Cp*W(NO)(η2-CH2═CHCH2Me). Such η2-alkene complexes are isolable as their 18e PMe3 adducts when compounds 1–3 are thermolyzed in neat PMe3, the other organometallic products formed during these thermolyses being Cp*W(NO)(PMe3)2 (5) and, occasionally, Cp*W(NO)(H)(η1-allyl)(PMe3). All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses. |
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| College: |
Faculty of Science and Engineering |
| Issue: |
12 |
| Start Page: |
5915 |
| End Page: |
5929 |