New nickel(II) and iron(II) helicates and tetrahedra derived from expanded quaterpyridines
Glasson, Christopher R.K., Meehan, George V., Motti, Cherie A., Clegg, Jack K., Turner, Peter, Jensen, Paul, and Lindoy, Leonard F. (2011) New nickel(II) and iron(II) helicates and tetrahedra derived from expanded quaterpyridines. Dalton Transactions, 40. pp. 10481-10490.
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As an extension of prior studies involving the linear quaterpyridine ligand, 5,5'''-dimethyl-2,2':5',5'':2'',2'''-quaterpyridine 1, the synthesis of the related expanded quaterpyridine derivatives 2 and 3 incorporating dimethoxy-substituted 1,4-phenylene and tetramethoxy-substituted 4,4'-biphenylene bridges between pairs of 2,2'-bipyridyl groups has been carried out via double-Suzuki coupling reactions between 5-bromo-5'-methyl-2'-bipyridine and the appropriate di-pinacol-diboronic esters using microwave heating. Reaction of 2 and 3 with selected Fe(II) or Ni(II) salts yields a mixture of both [M2L3]4+ triple helicates and [M4L6]8+ tetrahedra, in particular cases the ratio of the products formed was shown to be dependent on the reaction conditions; the respective products are all sufficiently inert to allow their chromatographic separation and isolation. Longer reaction times and higher concentrations were found to favour tetrahedron formation. The X-ray structures of solvated [Ni2(2)3](PF6)4, [(PF6) ⊂ Fe4(2)6](PF6)7, [Fe4(3)6](PF6)8 and [Ni4(3)6](PF6)8 have been determined, while the structure of the parent Fe(II) cage in the series, [(PF6) ⊂ Fe4(1)6](PF6)7, was reported previously. The internal volumes of the Fe(II) tetrahedral cages have been calculated and increase from 102 Å3 for [Fe4(1)6]8+ to 227 Å3 for [Fe4(2)6]8+ to 417 Å3 for [Fe4(3)6]8+ and to an impressive 839 Å3 for [Ni4(3)6]8+. The corresponding void volume in the triple helicate [Ni2(2)3]4+ is 29 Å3.
|Item Type:||Article (Refereed Research - C1)|
|Date Deposited:||08 May 2012 01:37|
|FoR Codes:||03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 40%
03 CHEMICAL SCIENCES > 0303 Macromolecular and Materials Chemistry > 030302 Nanochemistry and Supramolecular Chemistry @ 50%
03 CHEMICAL SCIENCES > 0305 Organic Chemistry > 030503 Organic Chemical Synthesis @ 10%
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