Complex halides of the transition metals.  XXI.  Evidence for the existence of tertiary phosphine derivatives of the new octachlorohexamolybdate(2+) cluster cation

Hamer, A. D.; Smith, Thomas J.; Walton, Richard A.

doi:10.1021/ic50159a005

Cited by 28 publications

(5 citation statements)

References 36 publications

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“…Triphenylphosphine and diphenylethylphosphine will form adducts with the cluster, but with triethylphosphine or diethylphenylphosphine reduction was found to occur [40], The cluster was also reduced by tri-n-propylphosphine in these latter experiments, in contrast to the result claimed above. The cesium salt is prepared analogously [43].…”

Section: Formation Of Adductscontrasting

confidence: 69%

“…Hamer and co-workers showed that the cluster can be chemically reduced with trialkylphosphines (triethyl-, diethylphenyl-, and tri-n-propylphosphine). The triethylphosphine derivative was characterized and formulated as [40]. The result for the tri-n-propylphosphine derivative is in disagreement with the results of Saito et al [39].…”

Section: Formation Of Adductsmentioning

confidence: 77%

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Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

Spink

1990

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Section: Formation Of Adductscontrasting

confidence: 69%

Section: Formation Of Adductsmentioning

confidence: 77%

Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

Spink

1990

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“…The extended cluster array is broken by donor ligands, L, to give Mo 6 Cl 12 L 2 species. The clusters are extremely versatile sensitizers for polymer modification since any nucleophilic ligand can serve to axially coordinate the hexanuclear core including amine, phosphine, − alcohol, triflate, and alkoxide donor ligands . Indeed, the axial coordination sites have been used to covalently attach the cluster core to the siloxide backbone of sol−gel glasses and recently to silica gel and poly(vinylpyridine)…”

Section: Introductionmentioning

confidence: 99%

Efficient Singlet Oxygen Generation from Polymers Derivatized with Hexanuclear Molybdenum Clusters

et al. 1996

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The molybdenum(II) chloride cluster Mo 6 Cl 12 has been immobilized on 2% cross-linked poly(4-vinylpyridine) (PVP-Mo 6 Cl 12 ) by the axial ligation of two pendant pyridines of the polymer to the hexanuclear metal core. Polymers with different cluster loadings exhibit the characteristic broad band emission of Mo 6 Cl 12 at λ max ) 765 ( 3 nm, and luminescence decays are composed of short-and long-lifetime components, which are consistent with the presence of cis-and trans-disubstituted cluster species, respectively. The lifetime of the cis form is too short to permit its bimolecular reaction with oxygen. However, the long-lifetime component is quenched efficiently by O 2 , and Stern-Volmer analyses of emission lifetimes yield quenching rate constants of (2-10) × 10 5 M -1 s -1 for cluster loadings in the range (3.5-0.3) × 10 -3 g/g of PVP, respectively. The quenching rate constant increases to ∼50 × 10 5 M -1 s -1 for all polymers in MeOH regardless of cluster loading. In aqueous solutions (pH 3-6) intermediate quenching rate constants are observed. These results correlate with the swelling properties of the PVP polymer in various solvents where greater swelling is manifested in greater accessibility of oxygen to the cluster active site and hence increased quenching rate constants. Oxygenated solutions of PVP-Mo 6 Cl 12 and alkenes photoreact to yield oxidized olefins. The products and product distributions indicate an energy transfer quenching reaction between oxygen and electronically excited polymer-bound clusters to produce singlet oxygen.

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Section: Formation Of Adductscontrasting

confidence: 69%

Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

Spink

View full text Add to dashboard Cite

Complex halides of the transition metals. XXI. Evidence for the existence of tertiary phosphine derivatives of the new octachlorohexamolybdate(2+) cluster cation

Cited by 28 publications

References 36 publications

Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

Efficient Singlet Oxygen Generation from Polymers Derivatized with Hexanuclear Molybdenum Clusters

Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

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