Synthesis and Characterization of Platina-β-diketones

Steinborn, Dirk; Gerisch, Michael; Merzweiler, Kurt; Schenzel, Karla; Pelz, A.; Bögel, Horst; Magull, Jörg

doi:10.1021/om950963k

Cited by 46 publications

(43 citation statements)

References 21 publications

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“…The structure of the dinuclear platina-b-diketone 11 a was calculated in C i symmetry, as was also experimentally found; [21] the calculated (11 a) and experimental (11 exp ) structures are in a good agreement ( Figure 5, Table 5 …”

Section: Dinuclear Platina-b-diketone [Pt 2 a C H T U N G T R E N N Usupporting

confidence: 61%

How Strong Are Hydrogen Bonds in Metalla‐β‐diketones?

Steinborn¹,

Schwieger²

2007

Chemistry A European J

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The energies of the kinetically inert, electronically saturated Lukehart-type metalla-beta-diketone [Re{(COMe)2H}(CO)4] (9 a) and of the kinetically labile, electronically unsaturated platina-beta-diketones [Pt{(COMe)2H}Cl2]- (10 a), [Pt2{(COMe)2H}2(micro-Cl)2] (11 a), and [Pt{(COMe)2H}(bpy)]+ (12 a) have been calculated by DFT at the B3LYP/6-311++G(d,p) level using effective core potentials with consideration of relativistic effects for the transition metals. Analogously, energies of the requisite open (non-hydrogen-bonded) equilibrium conformers (9 b, 10 c, 11 b, 12 b) and energies which were obtained from the hydrogen-bonded conformers by rigid rotation of the OH group around the C--O bond by 180 degrees followed by relaxation of all bond lengths and angles (9 c, 10 d, 11 c, 12 d) have been calculated. These energies were found to be higher by 14.7/27.2 (9 b/9 c), 20.7/27.2 (10 c/10 d), 19.2/25.7 (11 b/11 c), and 9.4/19.6 kcal mol(-1) (12 b/12 d) than those of the intramolecularly O--HO hydrogen-bonded metalla-beta-diketones 9 a, 10 a, 11 a, and 12 a, respectively. In acetylacetone (Hacac), the generic organic analogue of metalla-beta-diketones, the energies of the most stable non-hydrogen-bonded enol isomer (6 b) and of the conformer derived from the H-bonded form by rigid rotation of the OH group by 180 degrees followed by subsequent relaxation of all bond lengths and angles (6 k) were found to be 10.9/16.1 kcal mol(-1) (6 b/6 k) higher compared to the intramolecularly O--HO bonded isomer 6 a. Thus, the hydrogen bonds in metalla-beta- diketones must be regarded as strong and were found to be up to twice as strong as that in acetylacetone. A linear relationship was found between the hydrogen-bond energies based on the rigidly rotated structures and the OO separation in the hydrogen-bonded structures. Furthermore, these energies were also found to be correlated with the electron densities at the OH bond critical points (rhobcp) in the O--HO bonds of metalla-beta-diketones 9 a, 10 a, 11 a, and 12 a (calculated using the AIM theory). The comparison of the energies of the doubly intermolecularly hydrogen-bonded dinuclear platina-beta-diketone [{Pt{(COMe)2H}(bpy)}2]2+ (14) with that of the mononuclear intramolecularly hydrogen-bonded cation [Pt{(COMe)2H}(bpy)]+ (12 a) showed that the intermolecular hydrogen bonds in 14 are weaker than the intramolecular hydrogen bond in 12.

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Section: Dinuclear Platina-b-diketone [Pt 2 a C H T U N G T R E N N Usupporting

confidence: 61%

How Strong Are Hydrogen Bonds in Metalla‐β‐diketones?

Steinborn¹,

Schwieger²

2007

Chemistry A European J

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“…Dinuclear platina-β-diketones [Pt 2 {(COR) 2 H} 2 (μ-Cl) 2 ] (R = alkyl) can be considered hydroxycarbene complexes, which are stabilized by intramolecular O-H···O hydrogen bonds to neighboring acyl ligands. Due to their electronic unsaturation (16-valence-electron complexes) and their kinetically labile ligand sphere, platina-β-diketones exhibit a unique reactivity and thus can be precursor complexes for the synthesis of a great variety of acyl platinum(II) and platinum(IV) complexes with bidentate N ∧ N, P ∧ P, S ∧ S, N ∧ O ligands.…”

Section: Introductionmentioning

confidence: 99%

“…[2] Recently we reported the reactivity of the platina-β-diketone 1 toward tris(pyrazolyl)borates [(pz) 3 BH] -and [(3,5-Me 2 pz) 3 BH] -, which are known as versatile anionic tridentate nitrogen-donor ligands (Scheme 1). [3] This type of ligand is well established in transition-metal chemistry and belongs to the manifold class of the scorpionate ligands.…”

Section: Introductionmentioning

confidence: 99%

Diacetylplatinum(II) and ‐platinum(IV) Complexes Bearing κ²‐ and κ³‐Coordinated Tris(pyrazolyl)methane Ligands: Investigations on the Synthesis, Fluxionality, and Reactivity in Relation to the Substitution Pattern of the Ligands

2013

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Keywords: Platinum / Tridentate ligands / Hydrogen bonds / Fluxionality / Ab initio calculationsReactions of the dinuclear platina-β-diketone [Pt 2 {(COMe) 2 -H} 2 (μ-Cl) 2 ] (1) with HC(pz) 3 and HC(3,5-Me 2 pz) 3 (pz = pyrazol-1-yl; 3,5-Me 2 pz = 3,5-dimethylpyrazol-1-yl) afforded cationic, thermally labile diacetyl(hydrido)platinum(IV) complexes [Pt(COMe) 2 H{(pz) 3 CH}]Cl (3a) and [Pt(COMe) 2 H-{(3,5-Me 2 pz) 3 CH}]Cl (3b) with κ 3 -coordinated tris(pyrazolyl)-methane ligands, which were found to react with NaOH or NEt 3 to yield neutral diacetylplatinum(II) complexes with κ 2 -coordinated tris(pyrazolyl)methane ligands {[Pt(COMe) 2 -{(pz) 3 CH}] (4a); [Pt(COMe) 2 {(3,5-Me 2 pz) 3 CH}] (4b)}. In 4a/b, a molecular rearrangement (decoordination of a pyrazolyl ring and coordination of the originally pendant one) has been found that has been investigated by variable-temperature 1 H NMR spectroscopic measurements (coalescence method) as well as by DFT calculations. Diacetylplatinum(II) complexes 4 were found to react in oxidative addition reactions with ROTf (R = H, Me; OTf = trifluoromethanesulfonate) and methyl iodide to yield cationic diacetylplatinum(IV) complexes of the type [Pt(COMe) 2 R{(pz) 3 CH}]X (R/X = H/OTf,

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“…More recently, extensive ongoing studies (see Section 2.1.1) by Steinborn and co-workers focused on dimeric platina-β-diketones, where the hydroxycarbene ligands are being stabilized by adjacent acyl ligands (Fig. 12, 17) [55,56]. The diplatinum bishydroxycarbene dimer is a suitable precursor to a wide range of alkoxycarbene and diacetylplatinum(II) complexes [41,57].…”

Section: Complexes Not Bridged By Carbene Substituents or Metal-metalmentioning

confidence: 99%

Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

Bezuidenhout

Lotz

Liles

et al. 2012

Coordination Chemistry Reviews

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Synthesis and Characterization of Platina-β-diketones

Cited by 46 publications

References 21 publications

How Strong Are Hydrogen Bonds in Metalla‐β‐diketones?

How Strong Are Hydrogen Bonds in Metalla‐β‐diketones?

Diacetylplatinum(II) and ‐platinum(IV) Complexes Bearing κ²‐ and κ³‐Coordinated Tris(pyrazolyl)methane Ligands: Investigations on the Synthesis, Fluxionality, and Reactivity in Relation to the Substitution Pattern of the Ligands

Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

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Synthesis and Characterization of Platina-β-diketones

Cited by 46 publications

References 21 publications

How Strong Are Hydrogen Bonds in Metalla‐β‐diketones?

How Strong Are Hydrogen Bonds in Metalla‐β‐diketones?

Diacetylplatinum(II) and ‐platinum(IV) Complexes Bearing κ2‐ and κ3‐Coordinated Tris(pyrazolyl)methane Ligands: Investigations on the Synthesis, Fluxionality, and Reactivity in Relation to the Substitution Pattern of the Ligands

Recent advances in the field of multicarbene and multimetal carbene complexes of the Fischer-type

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Product

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Diacetylplatinum(II) and ‐platinum(IV) Complexes Bearing κ²‐ and κ³‐Coordinated Tris(pyrazolyl)methane Ligands: Investigations on the Synthesis, Fluxionality, and Reactivity in Relation to the Substitution Pattern of the Ligands