Formation of [Cr(CO)x(Ph2PN(iPr)PPh2)]+Structural Isomers by Reaction of Triethylaluminum with a ChromiumN,N-Bis(diarylphosphino)amine Complex [Cr(CO)4(Ph2PN(iPr)PPh2)]+: An EPR and DFT Investigation

Carter, Emma ORCID: https://orcid.org/0000-0001-6691-2377, Cavell, Kingsley John, Gabrielli, William F., Hanton, Martin J., Hallett, Andrew Jon, McDyre, Lucia, Platts, James Alexis ORCID: https://orcid.org/0000-0002-1008-6595, Smith, David M. and Murphy, Damien Martin ORCID: https://orcid.org/0000-0002-5941-4879 2013. Formation of [Cr(CO)x(Ph2PN(iPr)PPh2)]+Structural Isomers by Reaction of Triethylaluminum with a ChromiumN,N-Bis(diarylphosphino)amine Complex [Cr(CO)4(Ph2PN(iPr)PPh2)]+: An EPR and DFT Investigation. Organometallics 32 (6) , pp. 1924-1931. 10.1021/om400029y

Full text not available from this repository.

Abstract

The interaction of triethylaluminum (TEA) with a solution of the paramagnetic Cr(I) bis(phosphine) complex [Cr(CO)41][Al(OC(CF3)3)4] (1 = Ph2PN(iPr)PPh2) has been studied using EPR and DFT. It was found that the TEA is responsible for the complete removal of all CO groups from the [Cr(CO)41]+ complex, producing the [Cr(1-bis-η6-arene)]+, and this reaction occurs via a dominant pathway involving a series of [Cr(CO)x1]+ (x < 4) intermediates, consistently including the cis-[Cr(CO)31]+ complex (species A) and the “piano-stool”-type [Cr(CO)21]+ complex (species C). A further [Cr(CO)21]+ intermediate complex (labeled species D, which is a structural isomer of species C) was also identified experimentally, suggesting a second pathway for TEA activation may also be operative. All of these paramagnetic complexes have been characterized by CW EPR, and the spin Hamiltonian parameters were verified using DFT. The distribution and type of [Cr(CO)x1]+ intermediates formed were found to be very sensitive to the experimental conditions, including the quantity and manner of TEA addition, the temperature of activation, and the aging time of the solution.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Cardiff Catalysis Institute (CCI) Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Funders:	EPSRC
Last Modified:	16 Oct 2024 10:18
URI:	https://orca.cardiff.ac.uk/id/eprint/46630

Citation Data

Cited 20 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item