Macrocyclic dimer of Fc(NHC(O)PPh2-AuCl)2 induced by aurophilic interactions, and chirality induction into Fc core

Matsutani, Takanari; Itazaki, Masumi; Akine, Shigehisa; Moriuchi, Toshiyuki

doi:10.1016/j.jorganchem.2020.121182

Cited by 4 publications

(2 citation statements)

References 25 publications

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“…The macrocyclic dimer gold(I) complex 45, induced by aurophilic Au(I)-Au(I) interactions, can be obtained by the reaction of 1,1'bis(phosphinecarboxamidyl)ferrocene with chloro(tetrahydrothiophene)gold(I) (Figure 23). [36] In the macrocyclic dimer gold(I) complex 45, homochiral PP, homochiral MM, and heterochiral PM macrocyclic dimers based on the helical chirality of the ferrocene moieties through intermolecular aurophilic Au(I)-Au(I) interactions are formed, wherein S-and R- conformational enantiomers based on axial chirality of the Au(I)-Au(I) axis induce P-and M-helical chirality of the ferrocene moieties, respectively. The phosphinecarboxamide binding sites of 45 can accommodate halide ion of ammonium salt.…”

Section: Cyclic Ferrocene-peptide Conjugates Based On Complexationmentioning

confidence: 99%

Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates

Moriuchi

2021

Eur J Inorg Chem

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Ferrocene has been utilized as an organometallic scaffold for more than 25 years, serving as a central reverse-turn unit with the inter-ring spacing of about 3.3 Å. A variety of ferrocenepeptide conjugates have been designed to construct protein secondary structures and demonstrate the chirality organization via hydrogen bonding. In general, the helical chirality of ferrocene moieties in acyclic ferrocene-peptide conjugates is induced by the absolute configuration of the α-carbon atom of an amino acid adjacent to the ferrocene unit. Cyclization regulations restrict conformational flexibility of the peptide chains, inducing inversion of the helical chirality based on the reordering of the hydrogen bonding interactions. In this Minireview article, the helical chirality of ferrocene moieties in cyclic ferrocene-peptide conjugates is focused on. Controlled helical chirality of ferrocene moieties in a series of ferrocene-peptide conjugates by adjusting conformational flexibility of the peptide chains through cyclization regulations is introduced.

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Section: Cyclic Ferrocene-peptide Conjugates Based On Complexationmentioning

confidence: 99%

Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates

Moriuchi

2021

Eur J Inorg Chem

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“…Recently, the transition-metal complex bearing 1,1′-bis(diphenylphosphinecarboxamidyl)ferrocene Fc(NHC(O)PPh 2 ) 2 as a ligand has been reported to exhibit unique properties. The tetranuclear Pt complex with six Fc(NHC(O)PPh 2 ) 2 has a hollow cage structure [ 25 ], and the macrocyclic dimer of Fc(NHC(O)PPh 2 -AuCl) 2 , induced by aurophilic interactions, shows helical chirality induction into the ferrocene core when using chiral proline methyl ester hydrochloride [ 26 ]. Although phosphinecarboxamide has attracted attention as a ligand, no examples have been reported comparing the ligand behavior of phosphinecarboxamide and its thiocarbonyl analog (phosphinecarbothioamides) with the same transition-metal complex precursor.…”

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confidence: 99%

Synthesis and Characterization of Phosphinecarboxamide and Phosphinecarbothioamide, and Their Complexation with Palladium(II) Complex

et al. 2022

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Reactions of isocyanates/isothiocyanates with primary and secondary phosphines without solvent at room temperature afforded phosphinecarboxamide/phosphinecarbothioamide, respectively, in excellent yields. Furthermore, palladium complex Pd(COD)Cl2 was allowed to react with Ph2PC(O)NHPh (1a) to afford [Pd{Ph2PC(O)NHPh-κP}2Cl2] (3). On the other hand, the reaction of Pd(COD)Cl2 with 1 eq. of Ph2PC(S)NHPh (2a) afforded [PdCl2{Ph2PC(S)NHPh-κP,S}] (4). In the case of a 1:2 molar ratio, [PdCl{Ph2PC(S)NHPh-κP,S}{Ph2PC(S)NHPh-κP}]Cl (5) was formed. The newly obtained compounds were fully characterized using multielement NMR measurements and elemental analyses. In addition, the molecular structures of Ph2PC(O)NH(CH2)2Cl (1j), Ph2PC(S)NHPh(4-Cl) (2c), and 3–5 were determined using single-crystal X-ray diffraction.

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Synthesis and Structural Characterisation of an N‐Phosphanyl Ferrocene Carboxamide and its Ruthenium, Rhodium and Palladium Complexes

et al. 2020

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Abstract[((Diphenylphosphanyl)amino)carbonyl]ferrocene (1) has been synthesized and coordinated to light platinum metals, ruthenium, rhodium and palladium, in diverse coordination modes. Specifically, compound 1 was used to prepare the following phosphane complexes, [(η6‐mes)RuCl2(1‐κP)], [(η5‐C5Me5)RhCl2(1‐κP)], trans‐[PdCl2(1‐κP)2], and [(LNC)PdCl(1‐κP)] (mes=mesitylene, LNC=[2‐(dimethylamino‐κN)methyl]phenyl‐κC1). They were subsequently converted into cationic O,P‐chelate complexes by halide abstraction with AgClO4 and into neutral O,P‐chelate complexes by deprotonation with potassium tert‐butoxide. All coordination compounds and phosphane chalcogenides 1E (P‐bound chalcogen atom E=O, S and Se), which were also synthesised, were structurally characterised using spectroscopic methods (IR, multinuclear NMR and ESI MS) and single‐crystal X‐ray diffraction analysis. The electrochemical behaviour of the prepared compounds was studied by cyclic voltammetry, and the (LNC)Pd‐1 complexes were further studied by Mössbauer spectroscopy.

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Macrocyclic dimer of Fc(NHC(O)PPh2-AuCl)2 induced by aurophilic interactions, and chirality induction into Fc core

Cited by 4 publications

References 25 publications

Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates

Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates

Synthesis and Characterization of Phosphinecarboxamide and Phosphinecarbothioamide, and Their Complexation with Palladium(II) Complex

Synthesis and Structural Characterisation of an N‐Phosphanyl Ferrocene Carboxamide and its Ruthenium, Rhodium and Palladium Complexes

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