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Diimine supported group 10 hydroxo, oxo, amido, and imido complexes

Singh, Anupam and Anandhi, Upendran and Cinellu, Maria Agostina and Sharp, Paul R. (2008) Diimine supported group 10 hydroxo, oxo, amido, and imido complexes. Dalton Transactions, Vol. 2008 (17), p. 2314-2327. eISSN 1477-9234. Article.

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DOI: 10.1039/b715663d

Abstract

A series of L2 = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, But2bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of [L2Pt(μ-OH)]22+ with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields [(L2Pt)2(μ-OH)(μ-O)]+ as purple (Bian) or red (But2bpy) solids. Excess KOH gives dark blue [(Bian)Pt(μ-O)]2. MeOTf addition to [(But2bpy)2Pt2(μ-OH)(μ-O)]+ gives [(But2bpy)2Pt2(μ-OH)(μ-OMe)]2+ while [(Bian)Pt(μ-O)]2 yields [(Bian)2Pt2(μ-OMe)(μ-O)]+. Treatment of [(Bian)Pt(μ-O)]2 with “(Ph3P)Au+” gives deep purple [(Bian)2Pt2(μ-O)(μ-OAuPPh3)]+ while (COD)Pt(OTf)2 gives a low yield of [(Bian)Pt3(μ-OH)3(COD)2](OTf)3. Ni(But2bpy)Cl2 and [(Ph3PAu)3(μ-O)]+ in a 3 : 2 ratio yield red [Ni3(But2bpy)3(μ-O)2]2+. M(But2bpy)Cl2 (M = Pd, Pt) and [(Ph3PAu)3(μ-O)]+ give [M(But2bpy)(μ-OauPPh3)]22+ and [Pd4(But2bpy)4(μ-OAuPPh3)]3+. Addition of ArNH2 to [M(But2bpy)(μ-OH)]22+ (M = Pd, Pt) gives [Pt2(But2bpy)2(μ-NHAr)(μ-OH)]2+ (Ar = Ph, 4-tol, 4-C6H4NO2) and [M(But2bpy)(μ-NHAr)]22+ (Ar = Ph, tol). Deprotonation of [Pt2(But2bpy)2(μ-NH-tol)(μ-OH)]2+ with 1,8-bis(dimethylamino)naphthalene or NaH gives [Pt2(But2bpy)2(μ-NH-tol)(μ-O)]+. Deprotonation of [Pt(But2bpy)(μ-NH-tol)]22+ with KOBut gives deep green [Pt(But2bpy)(μ-N-tol)]2. The triflate complexes M(But2bpy)(OTf)2 (M = Pd, Pt) are obtained from M(But2bpy)Cl2 and AgOTf. Treatment of Pt(But2bpy)(OTf)2 with water gives the aqua complex [Pt(But2bpy)(H2O)2](OTf)2.

Item Type:Article
ID Code:4267
Status:Published
Refereed:Yes
Uncontrolled Keywords:Transition metals, hydroxo complexes, oxo–chloro exchange
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Royal Society of Chemistry
eISSN:1477-9234
Deposited On:27 Jul 2010 12:38

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