Photoreduction of 1,2-Dichloroalkanes and 1,2-Dichloroalkenes by Tetrakis(diphenyl phosphato)dimolybdenum(II,II)

Tsui Ling C. Hsu, I-Jy Chang, Donald L. Ward, Daniel G. Nocera

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Abstract

The quadruply bonded metal-metal complex Mo2[O2P(OC6H5)2]4 reduces 1,2-dichloroalkanes and 1,2-dichloroalkenes upon its irradiation with visible light (λexc ≥ 495 nm). The inorganic product of the photochemistry in all cases is the MoIIMoIII mixed-valence binuclear complex Mo2[O2P(OC6H5)2]4+, which has been structurally characterized. Green prismatic crystals of the tetrafluoroborate salt are triclinic with a Pi space group: a = 10.917(8), b = 11.793(4), c = 12.430(4) Å; a = 63.45(2), β = 70.38(4), γ = 70.64(5)°; V= 1316.8(12) Å3; Z = 1. The structure was refined to values of R = 0.036 and Rw = 0.043. The Mo-Mo bond distance of 2.191 Å is 0.05 Å greater than its quadruple bond parent complex, Mo2[O2P(OC6H5)2]4·2THF. The mixed-valence dimer shows a vibrationally-structured δ → δ (2B1u2B2g) absorption band in the near-infrared spectral region (λmax = 1469 nm, t = 142 M−1 cm-1) with a 308-cm-1 energy spacing, which is consistent with a progression in the symmetric metal-metal stretching vibration. The mixed-valence complex is reversibly reduced and oxidized by one-electron (E1/2(Mo2(II,III/II,II) = +0.067 V and E1/2(Mo2(III,III/II,III) = +0.997 V vs SCE). The nature of the organic product resulting from Mo2 [Mo2P(OC6H5)2]4 photochemistry depends on the organic substrate. For 1,2-dichloroalkanes, photoreaction is facile and affords the olefin (ϕp(1,2-dichloroethane) = 0.029; ϕp(1,2-transdichlorocyclohexane) = 0.040), whereas photoreaction of 1,2-dichloroalkenes yields monohalogenated alkenes (ϕp-(1,2-cis-dichloroethylene) = 5.5 × 10−6; ϕp(o-dichlorobenzene) = 1.4 × 10−4).

Original languageEnglish
Pages (from-to)2932-2937
Number of pages6
JournalInorganic Chemistry
Volume33
Issue number13
DOIs
Publication statusPublished - 1994 Jun 1

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photochemical reactions
Photochemistry
Photochemical reactions
Metals
Alkenes
Dichloroethylenes
valence
metals
alkenes
Coordination Complexes
Vibration
Dimers
Stretching
Absorption spectra
products
Salts
progressions
Irradiation
Electrons
Infrared radiation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Photoreduction of 1,2-Dichloroalkanes and 1,2-Dichloroalkenes by Tetrakis(diphenyl phosphato)dimolybdenum(II,II). / Hsu, Tsui Ling C.; Chang, I-Jy; Ward, Donald L.; Nocera, Daniel G.

In: Inorganic Chemistry, Vol. 33, No. 13, 01.06.1994, p. 2932-2937.

Research output: Contribution to journalArticle

Hsu, Tsui Ling C. ; Chang, I-Jy ; Ward, Donald L. ; Nocera, Daniel G. / Photoreduction of 1,2-Dichloroalkanes and 1,2-Dichloroalkenes by Tetrakis(diphenyl phosphato)dimolybdenum(II,II). In: Inorganic Chemistry. 1994 ; Vol. 33, No. 13. pp. 2932-2937.
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title = "Photoreduction of 1,2-Dichloroalkanes and 1,2-Dichloroalkenes by Tetrakis(diphenyl phosphato)dimolybdenum(II,II)",
abstract = "The quadruply bonded metal-metal complex Mo2[O2P(OC6H5)2]4 reduces 1,2-dichloroalkanes and 1,2-dichloroalkenes upon its irradiation with visible light (λexc ≥ 495 nm). The inorganic product of the photochemistry in all cases is the MoIIMoIII mixed-valence binuclear complex Mo2[O2P(OC6H5)2]4+, which has been structurally characterized. Green prismatic crystals of the tetrafluoroborate salt are triclinic with a Pi space group: a = 10.917(8), b = 11.793(4), c = 12.430(4) {\AA}; a = 63.45(2), β = 70.38(4), γ = 70.64(5)°; V= 1316.8(12) {\AA}3; Z = 1. The structure was refined to values of R = 0.036 and Rw = 0.043. The Mo-Mo bond distance of 2.191 {\AA} is 0.05 {\AA} greater than its quadruple bond parent complex, Mo2[O2P(OC6H5)2]4·2THF. The mixed-valence dimer shows a vibrationally-structured δ → δ (2B1u ← 2B2g) absorption band in the near-infrared spectral region (λmax = 1469 nm, t = 142 M−1 cm-1) with a 308-cm-1 energy spacing, which is consistent with a progression in the symmetric metal-metal stretching vibration. The mixed-valence complex is reversibly reduced and oxidized by one-electron (E1/2(Mo2(II,III/II,II) = +0.067 V and E1/2(Mo2(III,III/II,III) = +0.997 V vs SCE). The nature of the organic product resulting from Mo2 [Mo2P(OC6H5)2]4 photochemistry depends on the organic substrate. For 1,2-dichloroalkanes, photoreaction is facile and affords the olefin (ϕp(1,2-dichloroethane) = 0.029; ϕp(1,2-transdichlorocyclohexane) = 0.040), whereas photoreaction of 1,2-dichloroalkenes yields monohalogenated alkenes (ϕp-(1,2-cis-dichloroethylene) = 5.5 × 10−6; ϕp(o-dichlorobenzene) = 1.4 × 10−4).",
author = "Hsu, {Tsui Ling C.} and I-Jy Chang and Ward, {Donald L.} and Nocera, {Daniel G.}",
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T1 - Photoreduction of 1,2-Dichloroalkanes and 1,2-Dichloroalkenes by Tetrakis(diphenyl phosphato)dimolybdenum(II,II)

AU - Hsu, Tsui Ling C.

AU - Chang, I-Jy

AU - Ward, Donald L.

AU - Nocera, Daniel G.

PY - 1994/6/1

Y1 - 1994/6/1

N2 - The quadruply bonded metal-metal complex Mo2[O2P(OC6H5)2]4 reduces 1,2-dichloroalkanes and 1,2-dichloroalkenes upon its irradiation with visible light (λexc ≥ 495 nm). The inorganic product of the photochemistry in all cases is the MoIIMoIII mixed-valence binuclear complex Mo2[O2P(OC6H5)2]4+, which has been structurally characterized. Green prismatic crystals of the tetrafluoroborate salt are triclinic with a Pi space group: a = 10.917(8), b = 11.793(4), c = 12.430(4) Å; a = 63.45(2), β = 70.38(4), γ = 70.64(5)°; V= 1316.8(12) Å3; Z = 1. The structure was refined to values of R = 0.036 and Rw = 0.043. The Mo-Mo bond distance of 2.191 Å is 0.05 Å greater than its quadruple bond parent complex, Mo2[O2P(OC6H5)2]4·2THF. The mixed-valence dimer shows a vibrationally-structured δ → δ (2B1u ← 2B2g) absorption band in the near-infrared spectral region (λmax = 1469 nm, t = 142 M−1 cm-1) with a 308-cm-1 energy spacing, which is consistent with a progression in the symmetric metal-metal stretching vibration. The mixed-valence complex is reversibly reduced and oxidized by one-electron (E1/2(Mo2(II,III/II,II) = +0.067 V and E1/2(Mo2(III,III/II,III) = +0.997 V vs SCE). The nature of the organic product resulting from Mo2 [Mo2P(OC6H5)2]4 photochemistry depends on the organic substrate. For 1,2-dichloroalkanes, photoreaction is facile and affords the olefin (ϕp(1,2-dichloroethane) = 0.029; ϕp(1,2-transdichlorocyclohexane) = 0.040), whereas photoreaction of 1,2-dichloroalkenes yields monohalogenated alkenes (ϕp-(1,2-cis-dichloroethylene) = 5.5 × 10−6; ϕp(o-dichlorobenzene) = 1.4 × 10−4).

AB - The quadruply bonded metal-metal complex Mo2[O2P(OC6H5)2]4 reduces 1,2-dichloroalkanes and 1,2-dichloroalkenes upon its irradiation with visible light (λexc ≥ 495 nm). The inorganic product of the photochemistry in all cases is the MoIIMoIII mixed-valence binuclear complex Mo2[O2P(OC6H5)2]4+, which has been structurally characterized. Green prismatic crystals of the tetrafluoroborate salt are triclinic with a Pi space group: a = 10.917(8), b = 11.793(4), c = 12.430(4) Å; a = 63.45(2), β = 70.38(4), γ = 70.64(5)°; V= 1316.8(12) Å3; Z = 1. The structure was refined to values of R = 0.036 and Rw = 0.043. The Mo-Mo bond distance of 2.191 Å is 0.05 Å greater than its quadruple bond parent complex, Mo2[O2P(OC6H5)2]4·2THF. The mixed-valence dimer shows a vibrationally-structured δ → δ (2B1u ← 2B2g) absorption band in the near-infrared spectral region (λmax = 1469 nm, t = 142 M−1 cm-1) with a 308-cm-1 energy spacing, which is consistent with a progression in the symmetric metal-metal stretching vibration. The mixed-valence complex is reversibly reduced and oxidized by one-electron (E1/2(Mo2(II,III/II,II) = +0.067 V and E1/2(Mo2(III,III/II,III) = +0.997 V vs SCE). The nature of the organic product resulting from Mo2 [Mo2P(OC6H5)2]4 photochemistry depends on the organic substrate. For 1,2-dichloroalkanes, photoreaction is facile and affords the olefin (ϕp(1,2-dichloroethane) = 0.029; ϕp(1,2-transdichlorocyclohexane) = 0.040), whereas photoreaction of 1,2-dichloroalkenes yields monohalogenated alkenes (ϕp-(1,2-cis-dichloroethylene) = 5.5 × 10−6; ϕp(o-dichlorobenzene) = 1.4 × 10−4).

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