| Autor: |
Natalie R. Bunn, Joanna K. Day, Liling Ooi, Natalie D. Coombs, Simon Aldridge, Deborah L. Kays |
| Rok vydání: |
2016 |
| Předmět: |
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| Popis: |
Substitution, abstraction and addition processes have been shown to be viable chemistries for the modification of ligand systems featuring heavier group 13 element donor atoms. Thus substitution of the bromide in Cp ∗ Fe(CO) 2 In(Br)Mes ∗ ( 1 ) can be carried out with retention of the Fe–In bond, using 1 equiv. of the aryloxide nucleophile [OC 6 H 4 t Bu-4] − to give Cp ∗ Fe(CO) 2 In(OC 6 H 4 t Bu-4)Mes ∗ ( 2 ). Structural and spectroscopic comparisons of 1 and 2 reveal that variation in the steric and/or π donor properties of the indyl ligand substituents have little effect on the nature of the Fe–In bond. Sequential reaction of [Cp ∗ Fe(CO) 2 ] 2 GaCl ( 3 ) with the halide abstraction agent Na [ BAr 4 f ] and 4-picoline in dichloromethane proceeds via the known two-coordinate gallium cation [ { Cp ∗ Fe ( CO ) 2 } 2 ( μ - Ga ) ] + [ BAr 4 f ] - ( 4 ). The net result is replacement of the gallium bound chloride substituent with a 4-picoline moiety, yielding [ { Cp ∗ Fe ( CO ) 2 } 2 ( μ - Ga · 4 pic ) ] + [ BAr 4 f ] - ( 5 ) via a two-step abstraction/addition process. 5 represents only the second structurally characterized complex containing a cationic three-coordinate gallium centre, and the first displaying bonds to a transition metal. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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