Mononuclear and multiply bridged dinuclear phthalocyaninates(1-/2-) of yttrium by solvent controlled condensation; Small solvent clusters as ligands

Green chlorophthalocyaninato(2-)yttrium(III), [Y(Cl)pc(2-)] forms when yttr ium chloride is heated with o-phthalonitrile in 1-chloronaphthalene. Black cis-di(chloro)-phthalocyaninato(1-)yttrium(III), (cis)[Y(Cl)(2)pc(-)] is ob tained as a stable intermediate by partial reduction. Both complexes are so luble in many O-donor solvents and pyridine. The solubility in water is rem arkable: [Y(Cl)pc(2-)] dissolves with green, (cis)[Y(Cl)(2)pc(-)] with red- violet color. Typical absorptions of the pc(2-) ligand are observed at 1480 0 and 29700 cm(-1). A solvent dependent monomer-dimer equilibrium is found for the pc(-) radical. The monomer with absorptions at 12100 and 19900 cm(- 1) is favored in non-polar solvents, while in polar solvents the dimer with absorptions at 8700, 13200 and 18600 cm(-1) is preferred. cis-Tri (dimethy l-formamide)chlorophthalocyaninato(2-)-yttrium(III) etherate (1) crystallis es from a solution of [Y(Cl)pc(2-)] in MeOH/dmf, cis-tetra (dimethylsulfoxi de) phthalocyaninato(2-)yttrium(III) chloride etherate methanol disolvate ( 2) from thf/dmso, mu -di(chloro)-mu -di < di(pyridine)(mu -water)> di(phtha locyaninato(2-)- yttrium(III)) (5) from py, and cis-(chloro)pyridine(triphe nylphosphine oxide) phthalocyaninato(2-)yttrium(III) semi-etherate (3) is o btained from a solution of [Y(Cl)pc(2-)] and triphenylphosphine oxide in py . 1 condenses in MeOH yielding a (1:1)-mixture (4) of mu -di (chloro)di < ( trans- (diwater-dimethanol)> < dimethanol > phthalocyaninato(2-)yttrium(III )) (4a) and mu -di(chloro)di(dimethylformamide < dimethanol > -phthalocyani nato(2-)yttrium(III)) (4b); co-ordinatively bound solvent clusters are in b rakets. The structures of 1-5 have been established by X-ray crystallograph y. Apart from 3 with hepta-co-ordinated yttrium, the metal ion prefers octa -co-ordination, and the bond arrangement around Y3+, is always a distorted quadratic antiprism. In the dinuclear complexes obtained by solvent control led condensation both antiprisms share an edge by two mu -Cl atoms in 4, wh ile in 5 the antiprisms are face-shared by two trans positioned mu -Cl atom s and mu -O atoms, respectively. In 5, the bent (b)< {py}(2)(mu -H2O)> clus ter is stabilised by a combined interplanar bonding of pyridine by short N . . .H-O bonds (d(N . . .O) = 2.664(7) Angstrom; 2.81(2) Angstrom) and stro ng van-der-Waals interactions with the ecliptic pc(2-) ligands. 4a and 4b c ontain the dimeric methanol cluster < (MeOH)(2)>, and 4a in addition the cy clic heterotetrameric trans-diwaterdimethanol cluster, trans-c < (H2O)(2)(M eOH)(2)> The neutral clusters co-ordinatively bound to the Y atom are compa red with structurally established cluster-anions of type < (OMe)(MeOH)> (-) , linear l < (OMe)(MeOH)(2)> (-), cyclic (c)< (OH)(3)(H2O)(3)> (3-) (b)< {H 2O}(2){mu -O}> (2-), and (b){H2O}(2)(mu -F)> (-).