Sterically crowded peri-substituted naphthalene phosphines and their PV derivatives
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Three sterically crowded peri-substituted naphthalene phosphines, Nap[PPh2][ER] (Nap=naphthalene-1,8-diyl; ER=SEt, SPh, SePh) 1–3 , which contain phosphorus and chalcogen functional groups at the peri positions have been prepared. Each phosphine reacts to form a complete series of PV chalcogenides Nap[P(E′)(Ph2)(ER)] (E′=O, S, Se). The novel compounds were fully characterised by using X-ray crystallography and multinuclear NMR spectroscopy, IR spectroscopy and MS. X-ray data for 1 , 2 , n O , n S , n Se (n=1–3) are compared. Eleven molecular structures have been analysed by naphthalene ring torsions, peri-atom displacement, splay angle magnitude, X⋅⋅⋅E interactions, aromatic ring orientations and quasi-linear arrangements. An increase in the congestion of the peri region following the introduction of heavy chalcogen atoms is accompanied by a general increase in naphthalene distortion. P⋅⋅⋅E distances increase for molecules that contain bulkier atoms at the peri positions and also when larger chalcogen atoms are bound to phosphorus. The chalcogenides adopt similar conformations that contain a quasi-linear E⋅⋅⋅PC fragment, except for 3 O , which displays a twist-axial-twist conformation resulting in the formation of a linear O⋅⋅⋅SeC alignment. Ab initio MO calculations performed on 2 O , 3 O , 3 S and 3 Se reveal Wiberg bond index values of 0.02 to 0.04, which indicates only minor non-bonded interactions; however, calculations on radical cations of 3 O , 3 S and 3 Se reveal increased values (0.14–0.19).
Knight , F R , Fuller , A , Buehl , M , Slawin , A M Z & Woollins , J D 2010 , ' Sterically crowded peri -substituted naphthalene phosphines and their P V derivatives ' Chemistry - A European Journal , vol 16 , no. 25 , pp. 7617-7634 . DOI: 10.1002/chem.201000454
Chemistry - A European Journal
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1002/chem.201000454
DescriptionThis work is funded by the EPSRC UK
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