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Structural and electrochemical aspects of tris(ferrocenyl/phenyl-ethynyl)phosphine ligated chalcogen bridged iron carbonyl clusters

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Title Structural and electrochemical aspects of tris(ferrocenyl/phenyl-ethynyl)phosphine ligated chalcogen bridged iron carbonyl clusters
 
Creator MATHUR, P
RAI, DK
JI, RS
PATHAK, B
BOODIDA, S
MOBIN, SM
 
Subject RUTHENIUM(II) TERPYRIDINE COMPLEXES
ONE-STEP SYNTHESES
CRYSTAL-STRUCTURE
1,1'-BIS(DIPHENYLPHOSPHINO)FERROCENE DPPF
FERROCENYLETHYNYL PHOSPHANES
COUPLING REACTIONS
MOLECULAR WIRES
METAL
LIGANDS
SE
 
Description Room temperature stirring of THF solution of [Fe3Se2(CO)(9)] and P(C2R)(3) (R = Ph, Fc), in presence of Me3NO center dot 2H(2)O, yield monosubstituted [Fe3Se2(CO)(8){P(C2R)(3)}] (1, R = Ph; 2, R = Fc) and disubstituted [Fe3Se2(CO)(7){P(C2R)(3)}(2)] (3, R = Ph; 4, R = Fc) clusters. Under similar conditions, reactions of [Fe3Te2(CO)(9)] yield disubstituted [Fe3Te2(CO)(7){P(C2R)(3)}(2)] (5, R = Ph; 6, R = Fc) and [Fe3Te2(CO)(8){P(C2R)(3)}(2)] (7, R = Ph; 8, R = Fc), consisting of an adduct of Fe(CO)(2){P(C2R)(3)}(2) and Fe2Te2(CO)(6) butterfly moieties. Further substitution of 2 with P(C2Ph)(3) forms a mixed disubstituted cluster, [Fe3Se2(CO)(7)P(C(2)Fc)(3)P(C2Ph)(3)] (9). Crystal structures of disubstituted clusters 3-5 reveal a rare syn orientation of phosphinoalkyne ligands attached to the equatorial position of both basal irons, which is stabilised by an intramolecular CH center dot center dot center dot pi interaction. DFT calculations also suggest that syn disubstituted products are thermodynamically most stable. Electrochemistry of tris(ferrocenylethynyl) phosphine containing clusters 2, 4, 8 and 9 has been studied by cyclic voltammetry, which shows cathodically shifted multielectron reversible oxidation of ferrocenyl groups.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-10-15T15:55:58Z
2014-10-15T15:55:58Z
2013
 
Type Article
 
Identifier RSC ADVANCES, 3(48)26025-26034
http://dx.doi.org/10.1039/c3ra44788j
http://dspace.library.iitb.ac.in/jspui/handle/100/15208
 
Language en