Complexes of Group 1 Salts with N,N′-Aromatic Bidentate Ligands, of Mononuclear (‘Molecular’) 1 : 2 Salt : Base Ratio

Crystallizations of simple group 1 metal salts MX with NW-bidentate aromatic ligands 1, 10-phenanth ro line ('phen') and the hindered 2,9-dimethyl,1,10-phenanthroline ('dmp'), as well as complexes of other forms and stoichiometries described in accompanying papers, have yielded a broad array of simple mononuclear adducts of 1:2(:n) MX : L (:S) stoichiometry from methanol solutions. One of these, NaBr : phen : MeOH (1:2:2) contains a sixcoordinate metal atom, being ionic [(MeOH)(2)Na(phen)(2)]Br, but the majority contain five-coordinate metal atoms, being either ionic (one example only, [(MeOH)Li(phen)(2)](ClMeOH)-Me-.) or neutral [XML2] species, the latter for the combinations MX : phen (M = Li, X = I, ClO4, tfs (equivalent to 'triflate', F3CSO3) (a new form), NO3; M = Na, X = Br, I, ClO4, NO3) and MX : dmp (M = Na, X = NCS, Br, I, PF6, ClO4; M = K, X = I), the (coordinating) polyatomic anions being unidentate, and the coordination geometries distorted trigonal bipyramidal.