From Alkynols to Alkynol Complexes. A Molecular Assembly Study
Organometallics. Bd. 16. H. 22. Washington, DC: American Chemical Society 1997 S. 4910 - 4919
Erscheinungsjahr: 1997
ISBN/ISSN: 1520-6041
Publikationstyp: Zeitschriftenaufsatz
Sprache: Englisch
Doi/URN: 10.1021/om970331t
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Inhaltszusammenfassung
The solid state supramolecular assembly of prop-2-yn-1-ol and alkynediol transition metal complexes of Pt and Mi has been examined in light of the intermolecular interactions and hydrogen-bonding patterns established by alkyne monoalcohols and diols in the solid state. The analysis has been based on the crystal structure determination of the alcohols 1,1-dimelthyl-3-tert-butylprop-2-yn-1-ol (1), tert-butylbis(ethyl)prop-2-yn-1-ol (2), tert-butylcyclohexylprop-2-yn-1-ol (3), and tetramethylalk...The solid state supramolecular assembly of prop-2-yn-1-ol and alkynediol transition metal complexes of Pt and Mi has been examined in light of the intermolecular interactions and hydrogen-bonding patterns established by alkyne monoalcohols and diols in the solid state. The analysis has been based on the crystal structure determination of the alcohols 1,1-dimelthyl-3-tert-butylprop-2-yn-1-ol (1), tert-butylbis(ethyl)prop-2-yn-1-ol (2), tert-butylcyclohexylprop-2-yn-1-ol (3), and tetramethylalkynediol (4), as well as of the complexes bis(t-butylcyclohexylprop-2-yn-1-ol)M(0) (M = Pt (6a) and Ni (6b) and bis(t-butylcyclopentylprop-2-yn-1-ol)Pt(0) (7), integrated with the data available in the Cambridge Structural Database, It has been shown that the most common hydrogen-bond pattern is that based on a tetramer of -OH groups forming a square, a rhombus, or an open butterfly, irrespective of the molecular complexity, Larger ring systems or chains are established depending on the steric bulk of the substituents on the prop-2-yn-1-ol. Intermolecular and intramolecular hydrogen bond distances have been shown to depend on the type of alcohols, differences having largely a steric origin. The change-in the Raman/IR stretching frequency of the C=C bond upon coordination of alkynediols to the metal centers has been examined for the nickel compounds and shown to provide a diagnostic tool for recognition of hydrogen-bond formation and typology. » weiterlesen» einklappen