Ligand effects on structural, protophilic and reductive features of stannylated dinuclear iron dithiolato complexes

The synthesis and characterization of Fe 2 (CO) 5 (L){μ-(SCH 2 ) 2 SnMe 2 } (L = PPh 3 ( 2 ) and P(OMe) 3 ( 3 )) derived from the parent hexacarbonyl complex Fe 2 (CO) 6 {μ-(SCH 2 ) 2 }SnMe 2 ( 1 ) are reported. Whereas 1 exhibits a unique planar structure, X-ray crystallography showed that the apic...

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Bibliographic Details
Published in:New journal of chemistry 2021-01, Vol.45 (1), p.36-44
Main Authors: Abul-Futouh, Hassan, Almazahreh, Laith R, Abaalkhail, Sara J, Görls, Helmar, Stripp, Sven T, Weigand, Wolfgang
Format: Article
Language:English
Subjects:
Carbon monoxide
Carbonyls
Coordination compounds
Crystallography
Fourier transforms
Infrared spectroscopy
Iron
Ligands
NMR
Nuclear magnetic resonance
Planar structures
Protonation
Reduction
Spectrum analysis
Voltammetry
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Summary:The synthesis and characterization of Fe 2 (CO) 5 (L){μ-(SCH 2 ) 2 SnMe 2 } (L = PPh 3 ( 2 ) and P(OMe) 3 ( 3 )) derived from the parent hexacarbonyl complex Fe 2 (CO) 6 {μ-(SCH 2 ) 2 }SnMe 2 ( 1 ) are reported. Whereas 1 exhibits a unique planar structure, X-ray crystallography showed that the apical orientation of L in complexes 2 and 3 results in a chair/boat conformation of the Fe 2 S 2 C 2 Sn fused six-membered rings, which is typical for diiron dithiolato complexes. In solution, NMR and FTIR spectroscopic techniques provide evidence for a dynamic process of apical-basal site exchange of the ligand L in 2 and 3 . Protonation experiments on 2 and 3 in MeCN using CF 3 CO 2 H, HCl or HBF 4 ·Et 2 O suggest enhanced protophilicity of the Fe-Fe bond due to the presence of the electron donor ligands L as well as the stannylation effect. While the carbonyl ligands in 2 stretch at lower wavenumbers ν (CO) than those in 3 , the cyclic voltammetric reduction of 2 unpredictably occurs at less negative potential than that of 3 . In contrast to 1 , the presence of PPh 3 and P(OMe) 3 in 2 and 3 , respectively, allows protonation prior to reduction as shown by FTIR spectroscopy and cyclic voltammetry. The synthesis and characterization of Fe 2 (CO) 5 (L){μ-(SCH 2 ) 2 SnMe 2 } (L = PPh 3 ( 2 ) and P(OMe) 3 ( 3 )) derived from the parent hexacarbonyl complex Fe 2 (CO) 6 {μ-(SCH 2 ) 2 }SnMe 2 ( 1 ) are reported.
ISSN:1144-0546
1369-9261
DOI:10.1039/d0nj04790b