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Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide.

ABSTRACT: We report a rare example of oxygen atom transfer (OAT) from a polyoxometalate cluster to a series of tertiary phosphanes. Addition of PR₃ (PR₃ = PMe₃, PMe₂Ph, PMePh₂, PPh₃) to a neutral methoxide-bridged polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V₆O₇(OMe)₁₂]⁰, results in isolation of a reduced structure with phosphine oxide datively coordinated to a site-differentiated V^III ion. A positive correlation between the steric and electronic properties of the phosphane and the reaction rate was observed. Further investigation of the steric influence of the alkoxy-bridged clusters on OAT was probed through the use of POV clusters with bridging alkoxide ligands of varying chain length ([V₆O₇(OR')₁₂]; R' = Et, ⁿ Pr). These investigations expose that steric hinderance of the vanadyl moieties has significant influence on the rate of OAT. Finally, we report the reactivity of the reduced POV-alkoxide clusters with styrene oxide, resulting in the deoxygenation of the substrate to generate styrene. This result is the first example of epoxide deoxygenation using homometallic polyoxometalate clusters, demonstrating the potential for mono-vacant Lindqvist clusters to catalyze the removal of oxygen atoms from organic substrates.

SUBMITTER: Petel BE

PROVIDER: S-EPMC6837047 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide.

Petel Brittney E BE Meyer Rachel L RL Brennessel William W WW Matson Ellen M EM

Chemical science 20190715 34

We report a rare example of oxygen atom transfer (OAT) from a polyoxometalate cluster to a series of tertiary phosphanes. Addition of PR3 (PR3 = PMe3, PMe2Ph, PMePh2, PPh3) to a neutral methoxide-bridged polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V6O7(OMe)12]0, results in isolation of a reduced structure with phosphine oxide datively coordinated to a site-differentiated VIII< ...[more]

PMID: 31853359

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Project description:Nitrate reductases (NRs) are molybdoenzymes that reduce nitrate (NO3 -) to nitrite (NO2 -) in both mammals and plants. In mammals, the salival microbes take part in the generation of the NO2 - from NO3 -, which further produces nitric oxide (NO) either in acid-induced NO2 - reduction or in the presence of nitrite reductases (NiRs). Here, we report a new approach of VCl3 (V3+ ion source) induced step-wise reduction of NO3 - in a CoII-nitrato complex, [(12-TMC)CoII(NO3 -)]+ (2,{CoII-NO3 -}), to a CoIII-nitrosyl complex, [(12-TMC)CoIII(NO)]2+ (4,{CoNO}8), bearing an N-tetramethylated cyclam (TMC) ligand. The VCl3 inspired reduction of NO3 - to NO is believed to occur in two consecutive oxygen atom transfer (OAT) reactions, i.e., OAT-1 = NO3 - → NO2 - (r1) and OAT-2 = NO2 - → NO (r2). In these OAT reactions, VCl3 functions as an O-atom abstracting species, and the reaction of 2 with VCl3 produces a CoIII-nitrosyl ({CoNO}8) with VV-Oxo ({VV[double bond, length as m-dash]O}3+) species, via a proposed CoII-nitrito (3, {CoII-NO2 -}) intermediate species. Further, in a separate experiment, we explored the reaction of isolated complex 3 with VCl3, which showed the generation of 4 with VV-Oxo, validating our proposed reaction sequences of OAT reactions. We ensured and characterized 3 using VCl3 as a limiting reagent, as the second-order rate constant of OAT-2 (k 2 /) is found to be ∼1420 times faster than that of the OAT-1 (k 2) reaction. Binding constant (K b) calculations also support our proposition of NO3 - to NO transformation in two successive OAT reactions, as K b(CoII-NO2 -) is higher than K b(CoII-NO3 -), hence the reaction moves in the forward direction (OAT-1). However, K b(CoII-NO2 -) is comparable to K b{CoNO}8 , and therefore sequenced the second OAT reaction (OAT-2). Mechanistic investigations of these reactions using 15N-labeled-15NO3 - and 15NO2 - revealed that the N-atom in the {CoNO}8 is derived from NO3 - ligand. This work highlights the first-ever report of VCl3 induced step-wise NO3 - reduction (NRs activity) followed by the OAT induced NO2 - reduction and then the generation of Co-nitrosyl species {CoNO}8.

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

Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide.

Publications

Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphanes and deoxygenation of styrene oxide.

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