| 18414757 |
Singh A, Anandhi U, Cinellu MA, Sharp PR: Diimine supported group 10 hydroxo, oxo, amido, and imido complexes. . Dalton Trans. 2008 May 7;(17):2314-27. Epub 2008 Mar 4.
A series of L (2) = diimine (Bian = bis (3,5-diisopropylphenylimino) acenapthene, Bu (t)(2) bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of [L (2) Pt (mu-OH)](2)(2+) with 1,8-bis (dimethylamino) naphthalene, NaH, or KOH yields [(L (2) Pt)(2)(mu-OH)(mu-O)](+) as purple (Bian) or red (Bu (t)(2) bpy) solids. Excess KOH gives dark blue [(Bian) Pt (mu-O)](2). MeOTf addition to [(Bu (t)(2) bpy)(2) Pt (2)(mu-OH)(mu-O)](+) gives [(Bu (t)(2) bpy)(2) Pt (2)(mu-OH)(mu-OMe)](2+) while [(Bian) Pt (mu-O)](2) yields [(Bian)(2) Pt (2)(mu-OMe)(mu-O)](+). Treatment of [(Bian) Pt (mu-O)](2) with "(Ph (3) P) Au (+)" gives deep purple [(Bian)(2) Pt (2)(mu-O)(mu-OAuPPh (3))](+) while (COD) Pt (OTf)(2) gives a low yield of [(Bian) Pt (3)(mu-OH)(3)(COD)(2)](OTf)(3). Ni (Bu (t)(2) bpy) Cl (2) and [(Ph (3) PAu)(3)(mu-O)](+) in a 3 : 2 ratio yield red [Ni (3)(Bu (t)(2) bpy)(3)(mu-O)(2)](2+). M (Bu (t)(2) bpy) Cl (2) (M = Pd, Pt) and [(Ph (3) PAu)(3)(mu-O)](+) give [M (Bu (t)(2) bpy)(mu-OAuPPh (3))](2)(2+) and [Pd (4)(Bu (t)(2) bpy)(4)(mu-OAuPPh (3))](3+). Addition of ArNH (2) to [M (Bu (t)(2) bpy)(mu-OH)](2)(2+) (M = Pd, Pt) gives [Pt (2)(Bu (t)(2) bpy)(2)(mu-NHAr)(mu-OH)](2+) (Ar = Ph, 4-tol, 4-C (6) H (4) NO (2)) and [M (Bu (t)(2) bpy)(mu-NHAr)](2)(2+) (Ar = Ph, tol). Deprotonation of [Pt (2)(Bu (t)(2) bpy)(2)(mu-NH-tol)(mu-OH)](2+) with 1,8-bis (dimethylamino) naphthalene or NaH gives [Pt (2)(Bu (t)(2) bpy)(2)(mu-NH-tol)(mu-O)](+). Deprotonation of [Pt (Bu (t)(2) bpy)(mu-NH-tol)](2)(2+) with KOBu (t) gives deep green [Pt (Bu (t)(2) bpy)(mu-N-tol)](2). The triflate complexes M (Bu (t)(2) bpy)(OTf)(2) (M = Pd, Pt) are obtained from M (Bu (t)(2) bpy) Cl (2) and AgOTf. Treatment of Pt (Bu (t)(2) bpy)(OTf)(2) with water gives the aqua complex [Pt (Bu (t)(2) bpy)(H (2) O)(2)](OTf)(2). |
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