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- Title
CO Substitution Reactions of Diiron Complexes [{(μ-SCH<sub>2</sub>)<sub>2</sub>X}Fe<sub>2</sub>(CO)<sub>6</sub>] and [{(μ-SeCH<sub>2</sub>)<sub>2</sub>X}Fe<sub>2</sub>(CO)<sub>6</sub>] (X = O, CH<sub>2</sub>) with Ph<sub>2</sub>PCl/Me<sub>3</sub>NO to Give Ph<sub>2</sub>PCl-, Ph<sub>2</sub>PNMe<sub>2</sub>-, and Ph<sub>2</sub>PP(=O)Ph<sub>2</sub>-Substituted Complexes Related to [FeFe] Hydrogenases
- Authors
Song, Li‐Cheng; Cao, Meng; Du, Zong‐Qiang; Feng, Zhan‐Heng; Ma, Zhen; Song, Hai‐Bin
- Abstract
Diiron carbonyl complex [{(μ-SCH2)2O}Fe2(CO)6] ( A) reacted with Ph2PCl and Me3NO in MeCN at room temperature to give the expected and unexpected Ph2PCl-, Ph2PNMe2-, and Ph2PP(=O)Ph2-substituted complexes [{(μ-SCH2)2O}Fe2(CO)5L] [ 1, L = Ph2PCl; 2, L = Ph2PNMe2; 3, L = Ph2PP(=O)Ph2], whereas complex [{(μ-SCH2)2CH2}Fe2(CO)6] ( B) reacted with Ph2PCl and Me3NO under similar conditions to afford only the unexpected complexes [{(μ-SCH2)2CH2}Fe2(CO)5L] [ 4, L = Ph2PNMe2; 5, L = Ph2PP(=O)Ph2]. Similarly, complex [{(μ-SeCH2)2O}Fe2(CO)6] ( C) reacted with Ph2PCl and Me3NO in MeCN at room temperature to give the unexpected complexes [{(μ-SeCH2)2O}Fe2(CO)5L] [ 6, L = Ph2PNMe2; 7, L = Ph2PP(=O)Ph2], and the corresponding unexpected complexes [{(μ-SeCH2)2CH2}Fe2(CO)5L] [ 8, L = Ph2PNMe2; 9, L = Ph2PP(=O)Ph2] were produced by the reaction of complex [{(μ-SeCH2)2CH2}Fe2(CO)6] ( D) with Ph2PCl and Me3NO under similar conditions. The structures of 1- 9 were characterized by elemental analysis and spectroscopy, and for 1- 5 and 7- 9 by X-ray crystallography. Possible pathways for the formation of the functionalized phosphine-substituted complexes 1- 9 have been suggested. Complexes 1- 9 can be regarded as models for [FeFe] hydrogenases as their structures are similar to the active site of [FeFe] hydrogenases, and some have been found to be catalysts for proton reduction to hydrogen in the presence of HOAc.
- Subjects
IRON carbonyl synthesis; IRON compound synthesis; X-ray crystallography; HYDROGENASE; PHOSPHINE synthesis; DENSITY functional theory
- Publication
European Journal of Inorganic Chemistry, 2014, Vol 2014, Issue 11, p1886
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201301553