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Investigations on Synthesis, Structure, and Properties of New Butterfly [2Fe2Se] Cluster Complexes Relevant to Active Sites of Some Hydrogenases.
- Source :
-
Organometallics . Oct2009, Vol. 28 Issue 20, p6121-6130. 10p. - Publication Year :
- 2009
-
Abstract
- As a continuation of our studies on biomimetic chemistry and butterfly cluster chemistry, two series of âclosedâ and âopenâ butterfly [2Fe2Se] cluster complexes have been prepared in satisfactory yields. Thus, treatment of Fe3(CO)12with (HSeCH2)2CHOH in toluene at reflux gave the expected âclosedâ butterfly [2Fe2Se] cluster complex [(μ-SeCH2)2CH(OH)]Fe2(CO)6(A), whereas the âopenâ butterfly cluster complex (μ-EtSe)[(μ-SeCH2CH(OH)(CH2Br)]Fe2(CO)6(B) was unexpectedly produced along with complex Avia a sequential reaction of (μ-Se2)Fe2(CO)6with Et3BHLi, followed by treatment with (BrCH2)2CHOH. The other âclosedâ and âopenâ cluster complexes 1â6could be further prepared by the hydroxy transformation and CO substitution reactions of complexes Aand B. For example, (i) reaction of Awith PPh3and decarbonylating agent Me3NO afforded PPh3-monosubstituted complex [(μ-SeCH2)2CH(OH)]Fe2(CO)5(PPh3) (1), (ii) further reaction of 1with the acylating agent PhC(O)Cl in the presence of Et3N produced the benzoate-functionalized complex [(μ-SeCH2)2CH(O2CPh)]Fe2(CO)5(PPh3) (2), (iii) treatment of Awith the phosphatizing agent Ph2PCl in the presence of Et3N or simply with PhPCl2yielded the phosphite-functionalized complexes [(μ-SeCH2)2CH(OPPh2-η1)]Fe2(CO)5(3) and [(μ-SeCH2)2CH(OPPhCl-η1)]Fe2(CO)5(4), and (iv) treatment of Bwith 4-pyridinecarboxylic chloride or Ph2PCl in the presence of Et3N resulted in formation of the âopenâ butterfly cluster complexes (μ-EtSe)[μ-SeCH2CH(CH2Br)(O2CC5H4N-4)]Fe2(CO)6(5) and (μ-EtSe)[μ-SeCH2CH(CH2Br)(OPPh2-η1)]Fe2(CO)5(6). All the new complexes have been characterized by elemental analysis and spectroscopy, as well as for A, 1â4, and 6by X-ray crystallography. Both 1H and 77Se NMR spectral studies demonstrated that complexes Band 5consist of three isomers of e-Et/a-R, e-Et/e-R, and a-Et/e-R, whereas complex 6exists only as one isomer of e-Et/a-R. On the basis of an electrochemical study, it was found that the âclosedâ and âopenâ complexes Aand Bcan catalyze the proton reduction of TsOH and HOAc to give hydrogen, respectively. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 02767333
- Volume :
- 28
- Issue :
- 20
- Database :
- Academic Search Index
- Journal :
- Organometallics
- Publication Type :
- Academic Journal
- Accession number :
- 44846883
- Full Text :
- https://doi.org/10.1021/om900572t