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Homologous ferrocene phosphines
Vosáhlo, Petr ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
Title: Homologous ferrocene phosphines Author: Bc. Petr Vosáhlo Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: This thesis describes the synthesis and coordination behaviour of ferrocene diphosphines derived from 1,1'-bis(diphenylphosphino)ferrocene (dppf). Dppf is one of the most succesful ferrocene ligands, which can be used in various metal-catalyzed reactions. This study aimed to prepare analogous ligands with one dialkylphosphino substituent and one (diphenylphosphino)methyl group. These ligands were oxidized by KSeCN to afford the corresponding phosphinoselenides. The phosphinoselenides were used to assess sigma-donor abilities by measuring the coupling constant 1 JSeP via 31 P NMR spectroscopy. Lastly, the coordination behaviour of these ligands in palladium complexes was studied. The homologous ligands usually formed a mixtures containing a chelate complex and dimeric species with trans- coordinated ligands. Key words: ferrocene, phosphines, homologous ligands, palladium(II) complexes, structure elucidation.
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Alternative synthesis of of 1-(diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene
Zábranský, Martin ; Štěpnička, Petr (advisor) ; Vojtíšek, Pavel (referee)
An alternative, more straightforward and effective method for the preparation of 1- (diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene was developed using 1-bromo- 1'-(diphenylphosphino)ferrocene as the starting material and Eschenmoser's salt as an aminomethylation agent. Purity of thus prepared phosphinoamine was verified by 1 H and 31 P NMR spectroscopy and by comparison of the data with those reported in the literature (M. E. Wright, Organometallics, 1990, 9, 853). The coordination chemistry of this compound was investigated in gold(I) complexes. Thus, chlorido[1-(diphenylphosphino)-1'-(N,N-dimethyl- aminomethyl)ferrocene]gold(I) complex was synthesized and converted to ill-defined [1- (diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene]gold(I) perchlorate by halogen abstraction with AgClO4. Protonization of the nitrogen atom in both compounds with hydrogen chloride yielded the corresponding hydrochlorides. It was shown that 1- (diphenylphosphino)-1'-(N,N-dimethylaminomethyl)ferrocene is coordinated as a simple phosphine in the resulting complexes while its amine nitrogen is protonated. All these complexes were characterized by means of 1 H, 31 P and 13 C NMR spectroscopy, mass spectroscopy with electrospray ionisation, elemental analysis and by single-crystal X-ray diffraction analysis.
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Reactivity of a ferrocene distibane
Antala, Jakub ; Štěpnička, Petr (advisor) ; Gyepes, Róbert (referee)
5 Title: Reactivity of ferrocene distibane Author: Jakub Antala Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Consultant: RNDr. Jiří Schulz, Ph.D. Abstract: The aim of this bachelor thesis is preparation of 1,1'-bis(diphenylstibino)ferrocene (L), an antimony analogue of the widely studied ligand 1,1'-bis(diphenylphosphino)ferrocene and study into its coordination properties. Two ruthenium(II) (1, 3) and two rhodium(III) complexes (2, 4) were prepaired, in which the ligand L coordinates as bridging or chelating ligand. Two ruthenium(II) and one rhodium(III) precursors with π-coordinated arene ligands were used for the preparation of complexes. When preparing chelate complexes, sodium hexafluorophosphate was also necessary. All complexes were characterised by NMR spectroscopy, mass spectrometry, elemental analysis and crystal structure was determined by X-ray structural analysis. The structures of the stibine complexes were compared with their analogs resulting from 1,1'-bis(diphenylphosphino)ferrocene. Key words: ferrocene, stibines, complexes, ruthenium, rhodium, structure elucidation
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Synthesis and catalytic properties of ferrocenophane phosphines
Škoch, Karel
6 Title: Sythesis and catalytic properties of ferrocenophane phosphines Author: Karel Škoch Institution: Faculty of Science, Charles University in Prague, Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Keywords: ferrocene, ferrocenophane, phosphine ligands, palladium, asymetric catalysis, aza- Morita-Baylis-Hillman reaction, asymetric allylic alkylation Abstract: This Thesis describes the preparation of five sterically and electronically different ferrocene phosphines, (R)-1,1'-[1-(diarylphosphino)propan-1,3-diyl]ferrocenes (R)-1a-e, and a study into their coordination and catalytic properties. The key precursor of the phosphine synthesis, chiral alcohol (R)-2, was prepared according to the procedure described in the literature. Alcohol (R)-2 was converted with retention of configuration to diarylphosphines (R)-1a-e in one-step reaction with trimethylsilylchloride and sodium iodide and then with the corresponding diarylphosphine. Phosphines 1a-e were characterized by NMR and MS methods. For the basic representative 1a the following palladium(II) complexes were prepared: [PdCl(LNC )(1a)] (10, LNC = 2-[(dimethylamino)methyl]phenyl-C1 ,N) and trans- [PdCl2(1a)2] (9a). In addition, the isomeric complex cis-[PdCl2(1a)2] (9b) was isolated from the reaction mixture after catalytic...
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Phosphinoferrocene amides and hydrazides
Solařová, Hana
Title: Phosphinoferrocene amides and hydrazides Author: Hana Solařová Department: Department of Inorganic Chemistry Supervisor: doc. RNDr. Petr Štěpnička, Ph.D. Abstract: While studying functionalized phosphinoferrocene ligands, we recently turned to phosphinoferrocene carboxamides. These donors already proved to be versatile ligands for coordination chemistry and catalysis. This led us to synthesize and study the archetypal representative, 1'-(diphenylphosphino)-1-carbamoylferrocene (5), and the corresponding hydrazide 6. PPh2 COOH Fe Hdpf PPh2 CONH2 Fe 5 PPh2 CONHNH2 Fe 6 This work describes the preparation of primary amide 5 and hydrazide 6 from 1'- (diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf) via the corresponding acylbenzo- triazole derivative. The hydrazide was alternatively obtained from Hdpf methylester and hydrazine hydrate. Both newly synthesized compounds were characterized by spectroscopic methods (NMR, IR, and MS) and elemental analysis, and their crystal structures were determined by single-crystal X-ray crystallography. The amide was further utilized in the preparation of several palladium complexes, which were characterized in a similar manner including X-ray crystallography. One palladium complex was obtained also from the hydrazide. However, the hydrazide was used mainly as a...
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Homologous ferrocene phosphines
Vosáhlo, Petr
Title: Homologous ferrocene phosphines Author: Bc. Petr Vosáhlo Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: This thesis describes the synthesis and coordination behaviour of ferrocene diphosphines derived from 1,1'-bis(diphenylphosphino)ferrocene (dppf). Dppf is one of the most succesful ferrocene ligands, which can be used in various metal-catalyzed reactions. This study aimed to prepare analogous ligands with one dialkylphosphino substituent and one (diphenylphosphino)methyl group. These ligands were oxidized by KSeCN to afford the corresponding phosphinoselenides. The phosphinoselenides were used to assess sigma-donor abilities by measuring the coupling constant 1 JSeP via 31 P NMR spectroscopy. Lastly, the coordination behaviour of these ligands in palladium complexes was studied. The homologous ligands usually formed a mixtures containing a chelate complex and dimeric species with trans- coordinated ligands. Key words: ferrocene, phosphines, homologous ligands, palladium(II) complexes, structure elucidation.
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Light platinum group metal complexes with a ferrocene N-phosphinoamide
Navrátil, Michal
Title: Light platinum group metal complexes with a ferrocene N-phosphinoamide Author: Bc. Michal Navrátil Department: Department of Inorganic chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: The aim of this diploma thesis is the preparation of coordination compounds containing ferrocene phosphinoamide FcCONHPPh2 (1, Fc = ferrocenyl), whose preparation was discussed in author's bachelor thesis. Twelve new complexes are described in this thesis, including their characterisation by NMR and infrared spectroscopy, elemental analysis and mass spectrometry. In all cases the crystal structure was determined. Two palladium(II), one rhodium(III) and one ruthenium(II) precursors were used for the preparation of the complexes with each providing three new compounds. A reaction of the precursors with phosphinoamide 1 yielded complexes, in which the phosphinoamide was P-coordinated. This compound was a precursor for the other two complexes. The first one was obtained by a reaction with silver(I) perchlorate producing a cationic P,O-chelate. The other was obtained by a reaction with potassium tert-butoxide resulting in neutral P,O- chelate. All twelve complexes were prepared with optimised yields. Keywords: ferrocene, amides, phosphines, palladium, rhodium, ruthenium, structure elucidation.
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Homologous ferrocene phosphines
Vosáhlo, Petr
Title: Homologous ferrocene phosphines Author: Bc. Petr Vosáhlo Department: Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: This thesis describes the synthesis and coordination behaviour of ferrocene diphosphines derived from 1,1'-bis(diphenylphosphino)ferrocene (dppf). Dppf is one of the most succesful ferrocene ligands, which can be used in various metal-catalyzed reactions. This study aimed to prepare analogous ligands with one dialkylphosphino substituent and one (diphenylphosphino)methyl group. These ligands were oxidized by KSeCN to afford the corresponding phosphinoselenides. The phosphinoselenides were used to assess sigma-donor abilities by measuring the coupling constant 1 JSeP via 31 P NMR spectroscopy. Lastly, the coordination behaviour of these ligands in palladium complexes was studied. The homologous ligands usually formed a mixtures containing a chelate complex and dimeric species with trans- coordinated ligands. Key words: ferrocene, phosphines, homologous ligands, palladium(II) complexes, structure elucidation.
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Light platinum group metal complexes with a ferrocene N-phosphinoamide
Navrátil, Michal
Title: Light platinum group metal complexes with a ferrocene N-phosphinoamide Author: Bc. Michal Navrátil Department: Department of Inorganic chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D., DSc. Abstract: The aim of this diploma thesis is the preparation of coordination compounds containing ferrocene phosphinoamide FcCONHPPh2 (1, Fc = ferrocenyl), whose preparation was discussed in author's bachelor thesis. Twelve new complexes are described in this thesis, including their characterisation by NMR and infrared spectroscopy, elemental analysis and mass spectrometry. In all cases the crystal structure was determined. Two palladium(II), one rhodium(III) and one ruthenium(II) precursors were used for the preparation of the complexes with each providing three new compounds. A reaction of the precursors with phosphinoamide 1 yielded complexes, in which the phosphinoamide was P-coordinated. This compound was a precursor for the other two complexes. The first one was obtained by a reaction with silver(I) perchlorate producing a cationic P,O-chelate. The other was obtained by a reaction with potassium tert-butoxide resulting in neutral P,O- chelate. All twelve complexes were prepared with optimised yields. Keywords: ferrocene, amides, phosphines, palladium, rhodium, ruthenium, structure elucidation.
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