Beyond phosphorus: synthesis, reactivity, coordination behaviour and catalytic properties of 1,1'-bis(diphenylstibino)ferrocene
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F23%3A10464679" target="_blank" >RIV/00216208:11310/23:10464679 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=vZOizXYVhf" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=vZOizXYVhf</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d2dt03770j" target="_blank" >10.1039/d2dt03770j</a>
Alternative languages
Result language
angličtina
Original language name
Beyond phosphorus: synthesis, reactivity, coordination behaviour and catalytic properties of 1,1'-bis(diphenylstibino)ferrocene
Original language description
Compared to their widely studied phosphine counterparts, ferrocene stibines have received only marginal attention thus far. This paper describes the synthesis of 1,1'-bis(diphenylstibino)ferrocene (1*), which is an antimony analogue of the ubiquitous dppf, and our investigations into the reactivity and coordination behaviour of this compound. Thus, distibine 1 was oxidised to stiboranes fc(SbPh2X2)(2) (X = Cl, 2*; F, 6*; fc = ferrocene-1,1'-diyl) and to stibine-stiborane Ph(2)SbfcSbPh(2)F(2) (5*). Compounds 2 and 6 were easily hydrolysed to produce ferrocenophanes fc[SbPh2XOSbPh2X] (X = Cl, 3*; F, 7*). Removing the halogen from 3 with silver(i) salts afforded the corresponding ferrocenophanes with O-bound oxyanions, fc[SbPh(2)ZOSbPh(2)Z] (Z = NO3, 4a*; ClO4, 4b*), which were alternatively prepared from 2 and also converted back to 2 by adding a chloride source. Through investigations into the coordination behaviour of distibine 1, the following compounds were isolated and characterised: [(μ-ClO4)(2){Ag(1-κ(2)Sb,Sb')}(2)] (8*), [Ag(1-κ(2)Sb,Sb')(2)]X (X = ClO4, 9a; SbF6, 9b*), [(μ(Sb,Sb')-1){(arene)MCl2}(2)] (10*, 11*) and [(arene)MCl(1-κ(2)Sb,Sb')][PF6] (12*, 13*; 10, 12: M/arene = Ru/η(6)-p-cymene, 11, 13; Rh/η(5)-C5Me5), [(η(5)-C5Me5)RuCl(1-κ(2)Sb,Sb')] (14), [MCl2(1-κ(2)Sb,Sb')] (M = Pd, 15*; Pt, 16*), [Pd(1-κ(2)Sb,Sb')(2)]X-2 (X = BF4, 17a; SbF6, 17b*), [Pd(η(2)-ma)(1-κ(2)Sb,Sb')] (18*; ma = maleic anhydride), [(μ(Sb,Sb')-1)(AuCl)(2)] (19*), and [Au(1-κ(2)Sb,Sb')(2)]X (X = AuCl2, 20a*; SbF6, 20b*). Inspection of the structural parameters suggested that complexes featuring 1 exhibit less sterically strained structures than their dppf analogues due to longer M-Sb and Sb-C bonds, which reduce crowding around the ligated metal centre. Cyclic voltammetry and DFT calculations revealed that the primary electrochemical oxidation of 1 is reversible and occurs at the ferrocene unit. Based on preliminary catalytic tests in Suzuki-Miyaura biaryl coupling, Pd-1 complexes exhibited a lower efficiency than their respective Pd-dppf analogues. (An asterisk indicates that the crystal structure has been determined.)
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
<a href="/en/project/GA21-02316S" target="_blank" >GA21-02316S: Ferrocene ligands with Sb-donor groups</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
52
Issue of the periodical within the volume
5
Country of publishing house
GB - UNITED KINGDOM
Number of pages
14
Pages from-to
1198-1211
UT code for WoS article
000900414800001
EID of the result in the Scopus database
2-s2.0-85144865950