Rational synthesis of supramolecular assemblies based on tetraplatinum units: synthesis, characterization, and selective substitution reactions of four different Pt4 clusters.

Four different types of square-planar Pt(4) clusters, trans-[Pt(4)(μ-OCOCH(3))(6)(μ-ArNCHNAr)(2)] (2: ArNCHNAr = N,N'-diarylformamidinate), [Pt(4)(μ-OCOCH(3))(7)(μ-ArNCHNAr)] (8), cis-[Pt(4)(μ-OCOCH(3))(6)(κ(4)-N(4)-DArBp)] (9: DArBp = 1,3-bis(arylbenzamidinate)propane), and [Pt(4)Cl(2)(μ-OCOCH(3))(5)(κ(4)-N(2),P(2)-dpfam)] (13: dpfam = N,N'-bis[(2-diphenylphosphino)phenyl]formamidinate), were successfully prepared by using selective substitution reactions of in-plane acetate ligands of [Pt(4)(μ-OCOCH(3))(8)] (1), which has four in-plane and four out-plane acetate ligands, with appropriate capping ligands. Fundamental substitution reactions of the remaining in-plane acetates with benzoic acid derivatives were also investigated. All newly prepared complexes were characterized from spectral and physical data and combustion analysis.

Stepwise and one-pot syntheses of Ir(III) complexes with imidazolium-based carbene ligands.

We report the preparation, crystal structure, electrochemistry, and emission properties of Ir(Cinsertion markC:)3, where Cinsertion markC: is an N-heterocyclic carbene ligand. Two synthetic approaches are introduced for generating Ir(III) complexes bearing imidazolium-based carbene ligands whose precursors are [pypiH2][Cl] (1a) (pyridyl[1,2-a]{2-phenylimidazol}-3-ylidene chloride) and [pympiH2][Cl] (1b) (pyridyl[1,2-a-{2-(p-methoxy)phenylimidazol}-3-ylidene chloride). The first method is a stepwise reaction: treatment of [Ir(mu-Cl)(COD)]2, where COD is 1,5-cyclooctadiene, with 4 equiv.

Di-μ-chlorido-bis-[bis-(η-cyclo-octene)iridium(I)].

The title complex, [Ir(2)(μ-Cl)(2)(C(8)H(14))(4)], has a dinuclear structure with bridging Cl atoms, a hinge angle of 179.44 (7)° between the two IrCl(2) planes, and an Ir⋯Ir distance of 3.7254 (3) Å.

Tetraplatinum precursors for supramolecular assemblies: syntheses, crystal structures, and stereoselective self-assemblies of [Pt4(micro-OCOCH3)6(kappa4-N4-DArBp)] (DArBp = 1,3-bis(arylbenzamidinate)propane).

Treatment of the cisoid-capped complex [Pt(4)(micro-OCOCH(3))(6)(kappa(4)-N(4)-DAr'Bp)] (), which was obtained from the reaction of [Pt(4)(micro-OCOCH(3))(8)] (1) with Na(2)D(t)BuPhBp (D(t)BuPhBp = 1,3-bis(para-tert-butylphenylbenzamidinate)propane), with an equimolar amount of 1,1'-ferrocenedicarboxylic acid undergoes a stereoselective self-assembly to afford an indented-quadrangle tetramer [Pt(4)(micro-OCOCH(3))(4)(kappa(4)-N(4)-D(t)BuPhBp){Fe(C(5)H(4)COO)(2)}](4) as a single diastereomer.

An infinite zigzag chain of alternating Cl-Pd-Pd-Cl and Mo-Mo units.

Treatment of Pd(2)Cl(2)(CNC(6)H(3)Me(2)-2,6)(4) (1) with Mo(2)(O(2)CCF(3))(4) (2) in dichloromethane afforded an infinite zigzag chain [[Pd(2)Cl(2)(CNC(6)H(3)Me(2)-2,6)(4)][Mo(2)(O(2)CCF(3))(4)]](n) (3), where two metal-metal bonded dinuclear Pd-Pd and Mo-Mo units were bridged by chloro atoms. The Mo-Mo distance (2.1312(3) A) of 3 is significantly elongated compared to that of 2 (2.

Facile Oxidative Addition of O-H Bonds of Methanol and Water to Ir Complexes Having Peraryldiphosphane Ligands.

A new piece in the puzzle. Hydrido(alkoxo) complexes of late transition metals have often been postulated as intermediates or transition states in the catalytic hydrogenation of carbonyl compounds and catalytic hydrogen transfer reactions. Here the facile oxidative addition of the O-H bonds of alcohol and water to iridium(I) complexes of peraryldiphosphanes [Eq.