Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)4(dppp)]+, by EPR Spectroscopy

Stephen L.J. Luckham; Andrea Folli; James A. Platts; Emma Richards; Damien M. Murphy

doi:10.1021/acs.organomet.9b00226

Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)₄(dppp)]⁺, by EPR Spectroscopy

Stephen L.J. Luckham
, Andrea Folli^*
, James A. Platts
, Emma Richards
, Damien M. Murphy

^*Corresponding author for this work

School of Chemistry

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

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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]⁺.

Original language	English
Journal	Organometallics
DOIs	https://doi.org/10.1021/acs.organomet.9b00226
Publication status	Published - 13 Jun 2019

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@article{3cb9828bcffd4cc5bbe1434c835d8fab,

title = "Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)4(dppp)]+, by EPR Spectroscopy",

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]+.",

author = "Luckham, \{Stephen L.J.\} and Andrea Folli and Platts, \{James A.\} and Emma Richards and Murphy, \{Damien M.\}",

year = "2019",

month = jun,

day = "13",

doi = "10.1021/acs.organomet.9b00226",

language = "English",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)4(dppp)]+, by EPR Spectroscopy

AU - Luckham, Stephen L.J.

AU - Folli, Andrea

AU - Platts, James A.

AU - Richards, Emma

AU - Murphy, Damien M.

PY - 2019/6/13

Y1 - 2019/6/13

N2 - 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]+.

AB - 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]+.

UR - https://www.scopus.com/pages/publications/85067974954

U2 - 10.1021/acs.organomet.9b00226

DO - 10.1021/acs.organomet.9b00226

M3 - Article (Academic Journal)

C2 - 32055085

AN - SCOPUS:85067974954

SN - 0276-7333

JO - Organometallics

JF - Organometallics

ER -

Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)₄(dppp)]⁺, by EPR Spectroscopy

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