Controlling Metal-to-Oxygen Ratios via M═O Bond Cleavage in Polyoxovanadate Alkoxide Clusters

Petel, Brittney E.; Fertig, Alex A; Maiola, Michela L.; Brennessel, William W.; Matson, Ellen M.

doi:10.1021/acs.inorgchem.9b00389

Cited by 20 publications

(69 citation statements)

References 40 publications

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“…S4†). 35 An additional absorbance is observed at 1163 cm –1 , assigned to ν (OP) for the bound OPMe 3 ligand (free OPMe 3 ; 1170 cm –1 ) 50. The similarities in energy between the ν (OP) of bound and dissociated OPMe 3 suggests complete OAT from the cluster to the substrate.…”

Section: Resultsmentioning

confidence: 98%

“…S1†). 35 Optimization of reaction conditions revealed that addition of 4 equiv. PMe 3 to 1 at 70 °C results in the complete consumption of the parent cluster after 19 hours (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Further support for complete OAT can be garnered from examination of V1–O c bond distances. Previously we have reported that reduced vanadium ions within oxygen-deficient POV-alkoxide clusters, [V 6 O 5 (OMe) 12 (MeCN) 2 ]35 and [V 6 O 6 (OMe) 12 OTf]34 (OTf = trifluoromethylsulfonate), possess a shortened V1–O c bond (O c = central oxygen atom, 2.0173 (avg) Å, 2.08(4) Å, respectively) and contracted V1–O b –V n bond angles (O b = bridging oxygen atom, avg ∼105°, Table S3†). Similar deviations in bond lengths and angles are observed in the X-ray structure of 2-OPMe 3 , with a V1–O c bond length of 2.120(5) Å and V1–O b –V n bond angles averaging ∼105°.…”

Section: Resultsmentioning

confidence: 99%

“…Bond valence sum (BVS) calculations revealed an oxidation state distribution of vanadium ions of V V VIV4V III , consistent with that reported for 2-MeCN (Table S2†). 35…”

Section: Resultsmentioning

confidence: 99%

“…All other solvents were dried and deoxygenated on a Glass Contour System (Pure Process Technology, LLC) and stored over activated 3 Å molecular sieves purchased from Fisher Scientific prior to use. [V 6 O 7 (OMe) 12 ] 0 ( 1 ),14 [V 6 O 6 (OMe) 12 ] 0 ( 2 ),35 [V 6 O 7 (OEt) 12 ] 0 ( 3 ),15 and [V 6 O 7 (O n Pr) 12 ] 0 ,62 were prepared according to published procedures. Trimethlyphosphine, dimethylphenylphosphine, triphenylphosphine, and propylene carbonate were purchased from Sigma Aldrich and used as received.…”

Section: Methodsmentioning

confidence: 99%

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

et al. 2019

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We report a rare example of oxygen atom transfer (OAT) from a polyoxometalate cluster to a series of tertiary phosphanes. Addition of PR 3 (PR 3 ¼ PMe 3 , PMe 2 Ph, PMePh 2 , PPh 3 ) to a neutral methoxidebridged polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V 6 O 7 (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 ([V 6 O 7 (OR 0 ) 12 ]; R 0 ¼ 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. † Electronic supplementary information (ESI) available: 1 H NMR, ESI-MS (+ve), UV-vis, and IR spectroscopic data for all complexes, crystallographic parameters and BVS calculations of complexes 2-OPMe 3 , 2-OPMe 2 Ph, 2-OPMePh 2 , 2-OPPh 3 , and 4-OPPh 3 , attempted synthesis of 4-OPMePh 2 , 4-OPPh 3 , and propoxide derivatives, 1 H NMR analysis of styrene oxide OAT reactions with 2-OPMe 3 and 4-OPMe 3 . For ESI and crystallographic data (CCDC1914250-1914254) in CIF or other electronic format see Scheme 1 Previously reported synthesis of the mono-vacant neutral cluster, 2-MeCN, via addition of VMes 3 (THF) addition (left) 35 and synthesis of [V 6 O 6 (OMe) 12 OPMe 3 ] (2-OPMe 3 ) via OAT to PMe 3 reported in this work (right). 8036 | Chem. Sci., 2019, 10, 8035-8045 This journal is Scheme 2 Synthesis of complexes 2-OPMe 2 Ph, 2-OPMePh 2 , and 2-OPPh 3 . 8038 | Chem. Sci., 2019, 10, 8035-8045 This journal is Scheme 3 Synthesis of complexes 4-OPMe 3 and 4-OPMe 2 Ph. This journal is Scheme 5 Stoichiometric oxygen atom transfer facilitated by an oxygen-atom vacancy on a POV-alkoxide cluster. 8040 | Chem. Sci., 2019, 10, 8035-8045 This journal is

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Section: Resultsmentioning

confidence: 98%

“…S1†). 35 Optimization of reaction conditions revealed that addition of 4 equiv. PMe 3 to 1 at 70 °C results in the complete consumption of the parent cluster after 19 hours (Fig.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…Bond valence sum (BVS) calculations revealed an oxidation state distribution of vanadium ions of V V VIV4V III , consistent with that reported for 2-MeCN (Table S2†). 35…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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