Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds

Reichl, Kyle D.; Mandell, Chelsea L.; Henn, Owen D.; Dougherty, William G.; Kassel, W. Scott; Nataro, Chip

doi:10.1016/j.jorganchem.2011.09.004

Cited by 9 publications

(4 citation statements)

References 42 publications

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“…The ferrocene units in 6a – d are tilted by less than 5°, except for the bulky tert -butyl derivative, in which the cyclopentadienyl planes subtend an angle of 7.2(1)°. The PSe bond lengths vary by less than approximately 0.02 Å in the entire series and compare well with the values reported for dppfSe 2 and analogous compounds . Likewise, the parameters describing the amide moieties do not substantially differ from those determined for 1d , 1c , and 5c (see above).…”

Section: Results and Discussionsupporting

confidence: 84%

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

et al. 2017

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The stereoelectronic influence of phosphine substituents on the coordination and catalytic properties of phosphinoferrocene carboxamides was studied for the model compounds R2PfcCONHMe (1a–d), where fc = ferrocene-1,1′-diyl and R = i-Pr (a), t-Bu (b), cyclohexyl (Cy; c), Ph (d), using experimental and DFT-computed parameters. The electronic parameters were examined via 1 J SeP coupling constants determined for R2P(Se)fcCONHMe (6a–d) and CO stretching frequencies of the Rh(I) complexes trans-[RhCl(CO)(1-κP)2] (7a–d); the steric properties of 1a–d were assessed through Tolman’s ligand cone angles (θ) and solid angles (Ω). Generally, a very good agreement between the calculated and experimental values was observed. Whereas the donor ability of the amidophosphines was found to increase from 1d through 1a,c to 1b, the trends in steric demand suggested by the two parameters differed, reflecting the different spatial properties of the phosphine substituents. In situ NMR studies and catalytic tests on the Suzuki–Miyaura cross-coupling of 4-bromoanisole with a bicyclic 4-tolylborate to give 4-methyl-4′-methoxybiphenyl using [Pd(η2:η2-cod)(η2-ma)] (cod = cycloocta-1,5-diene, ma = maleic anhydride) as a Pd(0) precursor revealed that different Pd-1 species (precatalysts) were formed from different ligands and participated in the reaction. Specifically, the bulky and electron-rich donor 1b favored the formation of [Pd(1b)(ma)], while the remaining ligands provided the corresponding bis-phosphine complexes [Pd(1)2(ma)]. The best results in terms of catalyst longevity and efficacy were observed for ligands 1a,c.

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Section: Results and Discussionsupporting

confidence: 84%

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

et al. 2017

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“…36 This 0.11 V difference is precisely the same difference observed for the reduction potentials of the free ligands, dppc + and dippc + (−1.14 and −1.25 V vs. FcH 0/+ respectively) in methylene chloride. 42 This suggests that the observed wave can be attributed to the reduction of Co(III) to Co(II). A correlation between the redox potentials of compounds containing 1,1′-bis( phosphino)ferrocene and 1,1′-bis( phosphino)cobaltocenium ligands has been developed.…”

Section: Resultsmentioning

confidence: 92%

Spectroscopic, structural and computational analysis of [Re(CO)₃(dippM)Br]ⁿ⁺ (dippM = 1,1′-bis(diiso-propylphosphino)metallocene, M = Fe, n = 0 or 1; M = Co, n = 1)

et al. 2016

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While the redox active backbone of bis(phosphino)ferrocene ligands is often cited as an important feature of these ligands in catalytic studies, the structural parameters of oxidized bis(phosphino)ferrocene ligands have not been thoroughly studied. The reaction of [Re(CO)3(dippf)Br] (dippf = 1,1'-bis(diiso-propylphosphino)ferrocene) and [NO][BF4] in methylene chloride yields the oxidized compound, [Re(CO)3(dippf)Br][BF4]. The oxidized species, [Re(CO)3(dippf)Br][BF4], and the neutral species, [Re(CO)3(dippf)Br], are compared using X-ray crystallography, cyclic voltammetry, visible spectroscopy, IR spectroscopy and zero-field (57)Fe Mössbauer spectroscopy. In addition, the magnetic moment of the paramagnetic [Re(CO)3(dippf)Br][BF4] was measured in the solid state using SQUID magnetometry and in solution by the Evans method. The electron transfer reaction of [Re(CO)3(dippf)Br][BF4] with acetylferrocene was also examined. For additional comparison, the cationic compound, [Re(CO)3(dippc)Br][PF6] (dippc = 1,1'-bis(diiso-propylphosphino)cobaltocenium), was prepared and characterized by cyclic voltammetry, X-ray crystallography, and NMR, IR and visible spectroscopies. Finally, DFT was employed to examine the oxidized dippf ligand and the oxidized rhenium complex, [Re(CO)3(dippf)Br](+).

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“…The manipulation of the phosphine substituent was reflected in the 31 P{ 1 H} NMR spectra (Table 1). Of particular note are the similarities in the 31 P NMR shifts determined for 3E (E = void, BH 3 , O, and S) and 5 to those for analogous “simple” compounds such as (dicyclohexylphosphino)ferrocene ( δ P −6.0) and its P -oxide ( δ P 46.8), 13 1,1′-bis(dicyclohexylphosphinothioyl)ferrocene (fc(P(S)Cy 2 ) 2 ; fc = ferrocene-1,1′-diyl, 14 δ P 57.3), 1-(dicyclohexylphosphino)-1′-methylferrocene–borane (1 : 1) (Cy 2 PfcMe·BH 3 ; δ P 24.1), 15 and the complex [{μ(P,P′)-fc(PCy 2 ) 2 }(AuCl) 2 ] ( δ P 41.2; all values in CDCl 3 ), 16 which ruled out any significant interactions between the stibine moiety and the phosphorus substituents in all cases.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, reactivity and coordination behaviour of a ferrocene phosphinostibine and intramolecular interactions in its P(v) and Sb(v) derivatives

Antala,

Schulz,

Císařová

et al. 2024

New J. Chem.

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Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds

Cited by 9 publications

References 42 publications

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Spectroscopic, structural and computational analysis of [Re(CO)₃(dippM)Br]ⁿ⁺ (dippM = 1,1′-bis(diiso-propylphosphino)metallocene, M = Fe, n = 0 or 1; M = Co, n = 1)

Synthesis, reactivity and coordination behaviour of a ferrocene phosphinostibine and intramolecular interactions in its P(v) and Sb(v) derivatives

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Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds

Cited by 9 publications

References 42 publications

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Spectroscopic, structural and computational analysis of [Re(CO)3(dippM)Br]n+ (dippM = 1,1′-bis(diiso-propylphosphino)metallocene, M = Fe, n = 0 or 1; M = Co, n = 1)

Synthesis, reactivity and coordination behaviour of a ferrocene phosphinostibine and intramolecular interactions in its P(v) and Sb(v) derivatives

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Spectroscopic, structural and computational analysis of [Re(CO)₃(dippM)Br]ⁿ⁺ (dippM = 1,1′-bis(diiso-propylphosphino)metallocene, M = Fe, n = 0 or 1; M = Co, n = 1)