Structural, Computational, and Spectroscopic Investigation of [Pd(kappa(3)-1,1 '-bis(di-tert-butylphosphino)ferrocenediyl)X](+) (X = Cl, Br, I) Compounds

The reaction of [Pd(dtbpf)Cl-2] (dtbpf = 1,1'-bis(di-tert-butylphosphino)ferrocene) with sodium bromide yields [Pd(dtbpf)Br] [Br], which displays an interaction between the iron and palladium atoms. The structure of this compound has been obtained and is compared to those of the previously reported [Pd(dtbpf)X](+) (X = Cl, I) analogues. Similar to [Pd(dtbpf)Cl](+), [Pd(dtbpf)Br](+) appears to undergo a solid-state isomerization at low temperature to a species in which the Fe Pd interaction is disrupted. In addition to H-1 and P-31{H-1} NMR and visible spectroscopy, the [Pd(dtbpf)X](+) (X = Cl, Br) compounds were also characterized by zero-field Fe-57 Mossbauer spectroscopy. DFT calculations on [Pd(dtbpf)X](+) (X = Cl, Br, I) show that the Fe-Pd interaction is weak and noncovalent and that the strength of the interaction decreases as the halide becomes larger. A related trend is noted in the potential at which oxidation of the iron center occurs; the larger the halide, the less positive the potential at which oxidation occurs. Finally, the catalytic activity of [Pd(dtbpf)X](+) (X = Cl, Br, I) in the arylation of an aromatic ketone was examined and compared to the activity of [Pd(dtbpf)Cl-2].

Title	Structural, Computational, and Spectroscopic Investigation of [Pd(kappa(3)-1,1 '-bis(di-tert-butylphosphino)ferrocenediyl)X](+) (X = Cl, Br, I) Compounds
Creator	Nataro, Chip
	Blass, B. L.
	Diaconescu, P. L.
	Sanchez, R. H.
	Kassel, W. S.
	Piro, N. A.
	Decker, V. A.
	Robinson, M. J.
Publisher	Organometallics
Academic Department	Chemistry
Division	Natural Sciences
Organization	Lafayette College
Date Issued	2016
Date Available	2022-01-05
Type	Article
Language	English
Bibliographic Citation	Blass, B. L. (2016) "Structural, Computational, and Spectroscopic Investigation of [Pd(kappa(3)-1,1 '-bis(di-tert-butylphosphino)ferrocenediyl)X](+) (X = Cl, Br, I) Compounds." Organometallics 35 (4): 462-470.
Standard Identifier	DOI 10.1021/acs.organomet.5b00889
Standard Identifier	Handle 10385/6m311q682
Permalink	http://hdl.handle.net/10385/6m311q682
Rights Statement	In Copyright
Rights Holders	American Chemical Society