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Template Synthesis of 1,4,7-Triphosphacyclononanes

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Contribution from the School of Chemistry, Cardiff University, Main Building, Cardiff CF10 3AT, United Kingdom
Cite this: J. Am. Chem. Soc. 2006, 128, 11, 3818–3830
Publication Date (Web):February 18, 2006
Copyright © 2006 American Chemical Society

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    Iron(II) templates based on a [(η5-CpR)Fe]+ core have been employed for the successful synthesis of 1,4,7-triphosphacyclononane derivatives (9-aneP3R‘3) from a range of appropriately functionalized coordinated diphosphines and monophosphines. 1,2-Diphosphinoethane (1,2-dpe) or (2-phosphinoethyl)phenylphosphine (Phdpe) undergo a base-catalyzed Michael-type addition to trivinylphosphine, divinyl(benzyl)phosphine, or divinyl(phenyl)phosphine in [(η5-CpR)Fe(diphosphine)(monophosphine)]+ complexes (2aj) to give [(η5-CpR)Fe(9aneP3R‘3)]+ derivatives (4aj) containing coordinated triphosphacyclononanes bearing one (with Phdpe) or two (with 1,2-dpe) secondary phosphine donors. The rates of macrocyclization show a dependence on the nature of the substituent(s) R on the cyclopentadienyl ligand with increased rates being observed along the series R = H5 < (Me3Si)H4 < 1,3-(Me3Si)2H3 ≈ Me5. For coupling reactions with trivinylphosphine, a pendant vinyl function remains in the macrocyclic product (4ag) which is readily hydrogenated to the corresponding ethyl derivatives (5ag). Further functionalization of coordinated secondary phosphines in the initially formed macrocycles (5ag) is achieved by proton abstraction followed by addition of the appropriate alkyl halide electrophile and gives rise to tritertiary-triphospha-cyclononanes (7ag, 7l, 7m). All new complexes have been fully characterized by spectroscopic and analytical methods in addition to the structural determination by single-crystal X-ray techniques of [{η5-(Me3Si)2C5H3)Fe(9-aneP3H2C2H3)]PF6, 4c, and [(η5-Me3SiC5H4)Fe(9-aneP3Et3)]BF4, 7b. 1,4,7-Triethyl-1,4,7-triphosphacyclononane is released from its metal template (7a, 7b) by treatment with either H2O2 or Br2/H2O to give the trioxide 9-aneP3(O)3Et3 (8). Attempts to recover the trivalent phosphorus species, 1,4,7-triethyl-1,4,7-triphosphacyclononane, from the trioxide by reduction proved unsuccessful.

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