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A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex.

ABSTRACT: Three new diruthenium oxyanion complexes have been prepared, crystallographically characterized, and screened for their potential to photochemically unmask a reactive Ru-Ru?O intermediate. The most promising candidate, Ru2(chp)4ONO2 (4, chp = 6-chloro-2-hydroxypyridinate), displays a set of signals centered around m/z = 733 amu in its MALDI-TOF mass spectrum, consistent with the formation of the [Ru2(chp)4O](+) ([6](+)) ion. These signals shift to 735 amu in 4*, which contains an (18)O-labeled nitrate. EPR spectroscopy and headspace GC-MS analysis indicate that NO2(•) is released upon photolysis of 4, also consistent with the formation of 6. Photolysis of 4 in CH2Cl2 at room temperature in the presence of excess PPh3 yields OPPh3 in 173% yield; control experiments implicate 6, NO2(•), and free NO3(-) as the active oxidants. Notably, Ru2(chp)4Cl (3) is recovered after photolysis. Since 3 is the direct precursor to 4, the results described herein constitute the first example of a synthetic cycle for oxygen atom transfer that makes use of light to generate a putative metal oxo intermediate.

SUBMITTER: Corcos AR

PROVIDER: S-EPMC5972014 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

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A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex.

Corcos Amanda R AR Pap József S JS Yang Tzuhsiung T Berry John F JF

Journal of the American Chemical Society 20160728 31

Three new diruthenium oxyanion complexes have been prepared, crystallographically characterized, and screened for their potential to photochemically unmask a reactive Ru-Ru═O intermediate. The most promising candidate, Ru2(chp)4ONO2 (4, chp = 6-chloro-2-hydroxypyridinate), displays a set of signals centered around m/z = 733 amu in its MALDI-TOF mass spectrum, consistent with the formation of the [Ru2(chp)4O](+) ([6](+)) ion. These signals shift to 735 amu in 4*, which contains an (18)O-labeled n ...[more]

PMID: 27406958

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Project description:The oxygen atom transfer reactivity of the dioxo-Mo(VI) complex, Tp(iPr)MoO(2)(OPh) (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate), with a range of tertiary phosphines (PMe(3), PMe(2)Ph, PEt(3), PBu(n)(3), PEt(2)Ph, PEtPh(2), and PMePh(2)) has been investigated. The first step in all the reactions follows a second-order rate law indicative of an associative transition state, consistent with nucleophilic attack by the phosphine on an oxo ligand, namely, Tp(iPr)MoO(2)(OPh) + PR(3) --> Tp(iPr)MoO(OPh)(OPR(3)). The calculated free energy of activation for the formation of the OPMe(3) intermediate (Chem. Eur. J. 2006, 12, 7501) is in excellent agreement with the experimental DeltaG() value reported here. The second step of the reaction, that is, the exchange of the coordinated phosphine oxide by acetonitrile, Tp(iPr)MoO(OPh)(OPR(3)) + MeCN --> Tp(iPr)MoO(OPh)(MeCN) + OPR(3), is first-order in starting complex in acetonitrile. The reaction occurs via a dissociative interchange (I(d)) or associative interchange (I(a)) mechanism, depending on the nature of the phosphine oxide. The activation parameters for the solvolysis of Tp(iPr)MoO(OPh)(OPMe(3)) (DeltaH(++) = 56.3 kJ mol(-1); DeltaS(++) = -125.9 J mol(-1) K(-1); DeltaG(++) = 93.8 kJ mol(-1)) and Tp(iPr)MoO(OPh)(OPEtPh(2)) (DeltaH(++) = 66.5 kJ mol(-1); DeltaS(++) = -67.6 J mol(-1) K(-1); DeltaG(++) = 86.7 kJ mol(-1)) by acetonitrile are indicative of I(a) mechanisms. In contrast, the corresponding parameters for the solvolysis reaction of Tp(iPr)MoO(OPh)(OPEt(3)) (DeltaH(++) = 95.8 kJ mol(-1); DeltaS(++) = 26.0 J mol(-1) K(-1); DeltaG(++) = 88.1 kJ mol(-1)) and the remaining complexes by the same solvent are indicative of an I(d) mechanism. The equilibrium constant for the solvolysis of the oxo-Mo(V) phosphoryl complex, [Tp(iPr)MoO(OPh)(OPMe(3))](+), by acetonitrile was calculated to be 1.9 x 10(-6). The oxo-Mo(V) phosphoryl complex is more stable than the acetonitrile analogue, whereas the oxo-Mo(IV) acetonitrile complex is more stable than the phosphoryl analogue. The higher stability of the Mo(V) phosphoryl complex may explain the phosphate inhibition of sulfite oxidase.

Dataset Information

A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex.

Publications

A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex.

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