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)

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 zerofield Fe-57 Mossbauer 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](+).

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)
Creator	Nataro, Chip
	Gramigna, K. M.
	Fey, N.
	Sanchez, R. H.
	Furneaux, A. G.
	Kassel, W. S.
	Piro, N. A.
	Robinson, M. J.
Publisher	Dalton Transactions
Academic Department	Chemistry
Division	Natural Sciences
Organization	Lafayette College
Date Issued	2016
Date Available	2022-01-05
Type	Article
Language	English
Bibliographic Citation	Furneaux, A. G., et al. (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.
Standard Identifier	Handle 10385/7m01bn20r
Standard Identifier	DOI 10.1039/c5dt04721h
Permalink	http://hdl.handle.net/10385/7m01bn20r
Rights Statement	In Copyright
Rights Holders	Royal Society of Chemistry