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)

Aliza G. Furneaux; Nicholas A. Piro; Raúl Hernández Sánchez; Kathryn M. Gramigna; Natalie Fey; Michael J. Robinson; W. Scott Kassel; Chip Nataro

doi:10.1039/c5dt04721h

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)

Aliza G. Furneaux, Nicholas A. Piro, Raúl Hernández Sánchez, Kathryn M. Gramigna, Natalie Fey, Michael J. Robinson, W. Scott Kassel, Chip Nataro^*

^*Corresponding author for this work

School of Chemistry

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Abstract

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 ⁵⁷Fe 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]⁺.

Original language	English
Pages (from-to)	4819-4827
Number of pages	9
Journal	Dalton Transactions
Volume	45
Issue number	11
Early online date	8 Feb 2016
DOIs	https://doi.org/10.1039/c5dt04721h
Publication status	Published - 21 Mar 2016

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Furneaux, A. G., Piro, N. A., Hernández Sánchez, R., Gramigna, K. M., Fey, N., Robinson, M. J., Kassel, W. S., & Nataro, C. (2016). 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). Dalton Transactions, 45(11), 4819-4827. https://doi.org/10.1039/c5dt04721h

@article{0df7b65cc3774503b921f248c27f5969,

title = "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)",

abstract = "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 57Fe M{\"o}ssbauer 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]+.",

author = "Furneaux, {Aliza G.} and Piro, {Nicholas A.} and {Hern{\'a}ndez S{\'a}nchez}, Ra{\'u}l and Gramigna, {Kathryn M.} and Natalie Fey and Robinson, {Michael J.} and Kassel, {W. Scott} and Chip Nataro",

year = "2016",

month = mar,

day = "21",

doi = "10.1039/c5dt04721h",

language = "English",

volume = "45",

pages = "4819--4827",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "11",

}

Furneaux, AG, Piro, NA, Hernández Sánchez, R, Gramigna, KM, Fey, N, Robinson, MJ, Kassel, WS & Nataro, C 2016, '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)', Dalton Transactions, vol. 45, no. 11, pp. 4819-4827. https://doi.org/10.1039/c5dt04721h

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). / Furneaux, Aliza G.; Piro, Nicholas A.; Hernández Sánchez, Raúl et al.
In: Dalton Transactions, Vol. 45, No. 11, 21.03.2016, p. 4819-4827.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - 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)

AU - Furneaux, Aliza G.

AU - Piro, Nicholas A.

AU - Hernández Sánchez, Raúl

AU - Gramigna, Kathryn M.

AU - Fey, Natalie

AU - Robinson, Michael J.

AU - Kassel, W. Scott

AU - Nataro, Chip

PY - 2016/3/21

Y1 - 2016/3/21

N2 - 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 57Fe 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]+.

AB - 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 57Fe 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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U2 - 10.1039/c5dt04721h

DO - 10.1039/c5dt04721h

M3 - Article (Academic Journal)

C2 - 26867513

AN - SCOPUS:84960405465

SN - 1477-9226

VL - 45

SP - 4819

EP - 4827

JO - Dalton Transactions

JF - Dalton Transactions

IS - 11

ER -

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)

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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)

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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)