Facile synthesis of mononuclear early transition-metal complexes of κ[superscript 3]cyclo-tetrametaphosphate ([P[subscript 4]O[subscript 12]][superscript 4−]) and cyclo-trimetaphosphate ([P[subscript 3]O[subscript 9]][superscript 3−])
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Cummins_Facile synthesis.pdf
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Author(s)
Manna, Cesar M.
Nassar, Mostafa Y.
Tofan, Daniel
Chakarawet, Khetpakorn
Cummins, Christopher C.
Alternative Title
Facile synthesis of mononuclear early transition-metal complexes of κ3cyclo-tetrametaphosphate ([P4O12]4−) and cyclo-trimetaphosphate ([P3O9]3−)
Date Issued
2014
Journal
Dalton Transactions
Publisher
Royal Society of Chemistry
Citation
Manna, Cesar M., Mostafa Y. Nassar, Daniel Tofan, Khetpakorn Chakarawet, and Christopher C. Cummins. “Facile Synthesis of Mononuclear Early Transition-Metal Complexes of Κ3cyclo-Tetrametaphosphate ([P4O12]4−) and Cyclo-Trimetaphosphate ([P3O9]3−).” Dalton Transactions 43, no. 4 (2013): 1509.
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Final published version
Abstract
We herein report the preparation of several mononuclear-metaphosphate complexes using simple techniques and mild conditions with yields ranging from 56% to 78%. Treatment of cyclo-tetrametaphosphate ([TBA]4[P4O12]·5H2O, TBA = tetra-n-butylammonium) with various metal sources including (CH3CN)3Mo(CO)3, (CH3CN)2Mo(CO)2(η3-C3H5)Cl, MoO2Cl2(OSMe2)2, and VOF3, leads to the clean and rapid formation of [TBA]4[(P4O12)Mo(CO)3]·2H2O, [TBA]3[(P4O12)Mo(CO)2(η3-C3H5)], [TBA]3[(P4O12)MoO2Cl] and [TBA]3[(P4O12)VOF2]·Et2O salts in isolated yields of 69, 56, 68, and 56% respectively. NMR spectroscopy, NMR simulations and single crystal X-ray studies reveal that the [P4O12]4− anion behaves as a tridentate ligand wherein one of the metaphosphate groups is not directly bound to the metal. cyclo-Trimetaphosphate-metal complexes were prepared using a similar procedure i.e., treatment of [PPN]3[P3O9]·H2O (PPN = bis(triphenylphosphine)iminium) with the metal sources (CH3CN)2Mo(CO)2(η3-C3H5)Cl, MoO2Cl2(OSMe2)2, MoOCl3, VOF3, WOCl4, and WO2Cl2(CH3CN)2 to produce the corresponding salts, [PPN]2[(P3O9)Mo(CO)2(η3-C3H5)], [PPN]2[(P3O9)MoO2Cl], [PPN]2[(P3O9)MoOCl2], [PPN]2[(P3O9)VOF2]·2CH2Cl2, and [PPN]2[(P3O9)WO2Cl] in isolated yields of 78, 56, 75, 59, and 77% respectively. NMR spectroscopy, NMR simulations and single-crystal X-ray studies indicate that the trianionic ligand [P3O9]3− in these complexes also has κ3 connectivity.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/c3dt52526k
