Acenaphtho[5,6-cd]-1,2-dichalcogenoles and their platinum complexes
| Autor: | David B. Cordes, Andrew Christopher Clifford Ward, Louise M. Diamond, J. Derek Woollins, Fergus R. Knight, Alexandra M. Z. Slawin |
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| Přispěvatelé: | University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, University of St Andrews. Office of the Principal |
| Jazyk: | angličtina |
| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
chemistry.chemical_element ComputingMilieux_LEGALASPECTSOFCOMPUTING DAS QD Chemistry Acenaphthylene Engineering and Physical Sciences Chalcogen Coordination complex Inorganic Chemistry chemistry.chemical_compound chemistry Research council ComputingMilieux_COMPUTERSANDEDUCATION Materials Chemistry Organic chemistry QD X-ray structure Physical and Theoretical Chemistry Platinum |
| Popis: | The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC). A related series of bis(phosphine) platinum complexes 1–5 and 6–8 bearing dichalcogenate acenaphthylene ligands have been synthesised. The chalcogen–chalcogen bonds in the parent acenaphtho[5,6-cd]-1,2-dichalcogenoles (AcenapylE2; L1 E = S, L2 E = Se; Acenapyl = acenaphthylene-5,6-diyl) were reduced with two equivalents of lithium triethylborohydride to form the dilithio-species. Metathetical addition of the lithium dichalcogenate species to a suspension of the appropriate cis-dichlorobis(phosphine)platinum in THF resulted in the formation of platinum(II) complexes [Pt(5,6-AcenapylE2)(PR3)2] (1 E = S, R3 = Ph3; 2 E = S, R3 = Ph2Me; 3 E = S, R3 = PhMe2; 4 E = S, R3 = Me3; 6 E = Se, R3 = Ph3; 7 E = Se, R3 = Ph2Me; 8 E = Se, R3 = PhMe2). The dilithio-species of L1 and L2 were also reacted with (1,5-cyclooctadiene)platinum(II) dichloride. This reaction was successful with L1 resulting in the formation of platinum complex [Pt(5,6-AcenapylS2)(COD)] (5). Complexes 1–3 and 5–8 have been fully characterised, principally by multinuclear magnetic resonance spectroscopy, IR and MS. Secondary isotopomer effects create complex satellite systems observed in both the 31P{1H} NMR and 77Se NMR spectra of selenium complexes 6–8. X-ray structures were determined for L1, 1, 3 and 6 and analysed, where appropriate, by measuring the peri-distance, splay angle magnitude, peri-atom displacement, central naphthalene ring torsions and the geometry around the platinum centre. Platinum was found to adopt a distorted square-planar geometry in all three complexes. Complex 1 was found to have the greatest molecular distortion of all three complexes, showing that changing the phosphine group and also the chalcogen has a noticeable effect. Comparisons were made between 6 and our previously reported [Pt(NapSe2)(PPh3)2] and [Pt(AcenapSe2)(PPh3)2] complexes; the level of distortion was found to decrease as the backbone is altered from naphthalene to acenaphthylene. Postprint |
| Databáze: | OpenAIRE |
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