Issue 48, 2013

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

Abstract

Room temperature stirring of THF solution of [Fe3Se2(CO)9] and P(C2R)3 (R = Ph, Fc), in presence of Me3NO·2H2O, 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)7P(C2Fc)3P(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⋯π 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.

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

Supplementary files

Article information

Article type
Paper
Submitted
30 Aug 2013
Accepted
16 Oct 2013
First published
16 Oct 2013

RSC Adv., 2013,3, 26025-26034

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

P. Mathur, D. K. Rai, R. S. Ji, B. Pathak, S. Boodida and S. M. Mobin, RSC Adv., 2013, 3, 26025 DOI: 10.1039/C3RA44788J

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