Luckham, Stephen L. J., Folli, Andrea  ORCID: https://orcid.org/0000-0001-8913-6606, Platts, James A. ORCID: https://orcid.org/0000-0002-1008-6595, Richards, Emma ORCID: https://orcid.org/0000-0001-6691-2377 and Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879
2019.
Unravelling the photochemical transformations of chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)4(dppp)]+, by EPR spectroscopy.
Organometallics
38
(12)
, -.
10.1021/acs.organomet.9b00226
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Abstract
UV-induced photochemical transformations of the paramagnetic [Cr(CO)4(Ph2PCH2CH2CH2PPh2)]+ complex (abbreviated [Cr(CO)4(dppp)]+) in dichloromethane was investigated by CW EPR spectroscopy. Room-temperature UV irradiation results in the rapid transformation of [Cr(CO)4(dppp)]+ into trans-[Cr(CO)2(dppp)2]+. However, low-temperature (77–120 K) UV irradiation reveals the presence of an intermediate mer-[Cr(CO)3(κ1-dppp)(κ2-dppp)]+ complex which photochemically transforms into trans-[Cr(CO)2(dppp)2]+. The derived spin Hamiltonian parameters for these complexes were confirmed by DFT calculations. The photoinduced reaction is shown to be concentration-dependent, leading to a distribution of the three complexes ([Cr(CO)4(dppp)]+, mer-[Cr(CO)3(κ1-dppp)(κ 2-dppp)]+, and trans-[Cr(CO)2(dppp)2]+). A bimolecular photoinduced mechanism is proposed to account for the formation of mer-[Cr(CO)3(κ1-dppp)(κ2-dppp)]+ and trans-[Cr(CO)2(dppp)2]+.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry Professional Services > Advanced Research Computing @ Cardiff (ARCCA) |
| Publisher: | American Chemical Society |
| ISSN: | 0276-7333 |
| Funders: | EPSRC |
| Date of First Compliant Deposit: | 18 June 2019 |
| Date of Acceptance: | 29 May 2019 |
| Last Modified: | 16 Oct 2024 10:20 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/123541 |
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