Dibenzylideneacetone Complexes of Transition Metals

Rubezhov, A. Z.

doi:10.1070/rc1988v057n12abeh003420

Cited by 13 publications

(8 citation statements)

References 103 publications

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“…Dibenzylidene acetone (dba‐H) is an electron‐deficient 1,4‐diene ligand that coordinates transition metals in a variety of modes, through either the olefin as a 1,4‐diene or bridging ligand, and/or carbonyl moieties, for example in [Rh(η 5 ‐C 5 Me 5 )(η 2 ,η 2 ‐dba‐H)]1 and [Fe(CO) 3 (η 4 ‐{(CO)(CHCH Ph) 2 })],2 in addition to other complexes (Fe,3 Ru,4 U5 complexes; selected examples are given in Figure 1). 6 [Pd 0 2 (dba‐H) 3 ] is the best known transition‐metal complex7 bearing a dba‐H ligand, and is a widely used Pd 0 precursor in synthetic chemistry, catalysis and organometallic chemistry. Related complexes, [Pd 0 2 (dba‐Z) 3 ] and [Pd 0 (dba‐Z) 2 ] (dba‐Z=dibenzylidene acetone with different Z‐substituents), have been reported 8.…”

Section: Introductionmentioning

confidence: 99%

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

Jarvis

Sehnal

Bajwa

et al. 2013

Chemistry A European J

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A multidentate and flexible diolefin-diphosphine ligand, based on the dibenzylidene acetone core, namely dbaphos (1), is reported herein. The ligand adopts an array of different geometries at Pt, Pd and Rh. At Pt(II) the dbaphos ligand forms cis- and trans-diphosphine complexes and can be defined as a wide-angle spanning ligand. (1)H NMR spectroscopic analysis shows that the β-hydrogen of one olefin moiety interacts with the Pt(II) centre (an anagostic interaction), which is supported by DFT calculations. At Pd(0) and Rh(I), the dbaphos ligand exhibits both olefin and phosphine interactions with the metal centres. The Pd(0) complex of dbaphos is dinuclear, with bridging diphosphines. The complex exhibits the coordination of one olefin moiety, which is in dynamic exchange (intramolecular) with the other "free" olefin. The Pd(0) complex of dbaphos reacts with iodobenzene to afford trans-[Pd(II)(dbaphos)I(Ph)]. In the case of Rh(I), dbaphos coordinates to form a structure in which the phosphine and olefin moieties occupy both axial and equatorial sites, which stands in contrast to a related bidentate olefin, phosphine ligand ("Lei" ligand), in which the olefins occupy the equatorial sites and phosphines the axial sites, exclusively.

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Section: Introductionmentioning

confidence: 99%

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

Jarvis

Sehnal

Bajwa

et al. 2013

Chemistry A European J

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“…Taking into account that Pd(dba) 2 exists in solution in the dimeric form Pd 2 (dba) 3 Solv [15], the following designations were used for description of the 1 H NMR spectra of Pd(dba) 2 . Three bridging bidentate dibenzylideneacetone ligands in the s-cis-s-trans-conformation were designated as dba(1), dba(2), dba(3), the alkene fragment of dibenzylideneacetone in the cis-position to the carbonyl group, as cis-alkene, in the trans-position, as trans-alkene.…”

Section: (Solv) + Dbamentioning

confidence: 99%

“…(dba) (М = Pd, Pt) with three bridging dibenzylideneacetone ligands in the s-cis, strans-conformation, where the molecule of dibenzylideneacetone is captured during crystallization instead of the molecule of the solvent. The binuclear structure of the Pd(dba) 2 complex is retained in the solution [15]. Pd 2 (dba) 3 (dba) + Solv ⇄ Pd 2 (dba) 3 …”

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Formation of palladium phosphides in the reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus

et al. 2012

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The reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus was studied using the methods of NMR, UV spectroscopy, and X-ray powder diffraction. The products of the reaction are shown to be palladium phosphides, their composition depending on the ratio of the reagents. The mechanism of the formation of the palladium-enriched phosphides is suggested, which includes the formation of palladium diphosphide PdP 2 that subsequently reacts with the excess of bis(dibenzylideneacetone)palladium(0) leading to palladium phosphides Pd 5 P 2 , Pd 3 P 0.8 , Pd 4.8 P, and free dibenzylideneacetone.increase the turnover number and turnover frequency in hydrogenation of alkenes almost by the order of magnitude [7,8]. The main reason of the promoting effect of white phosphorus on the catalytic properties of the system Pd(acac) 2 -Р 4 -Н 2 is the increase in the dispersity and stability of the formed nanoparticles [8]. The modifying effect of elemental phosphorus on the catalytic properties of palladium catalysts depends on a number of factors: the nature of the acidoligand in the precursor, reducer, concentration and the ratio of the reagents [9]. We believe that one of the reasons of the effect of the nature of the acidoligand on the properties of nanosized palladium catalysts modified with elemental phosphorus is the difference in the rates of reduction of Pd(II) to Pd(0), subsequent reaction of Pd(0) with elemental phosphorus, and clusterization of Pd(0). For the active in hydrogenation palladium catalysts modified with elemental phosphorus the following model was suggested: the core of the nanoparticle consists of palladium phosphides, mainly Pd 6 P, and its surface, of the active in the hydrogenation Pd(0) clusters.It is known that palladium phosphides can be obtained by various methods: the high temperature synthesis from the elements [10], thermal decomposition of organometallic precursors, in particular, phosphine complexes formed in situ from the metal salt and

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“…The precursors potentially suitable for the CVD of RuO2 and Ru films are ruthenium carbonyls, ruthenium carbonyl halides, ruthenocene, ruthenium I 3-diketonates and some of their organic and coordination derivatives [7]. However, the thermal decompositions of ruthenium carbonyl and ruthenium carbonyl chlorides, like those of the analogous platinum metal derivatives, are accompanied by severe corrosion of the equipment and the support materials.…”

Section: Introductionmentioning

confidence: 99%

Investigation of thermal properties of ruthenium(III) Β-diketonate precursors for preparation of RuO2 films by CVD

Bykov

Морозова

Игуменов

et al. 1996

Journal of Thermal Analysis

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By means of a tensimetric flow method and a static method with a silica-membrane zero gauge, the dependence of vapour pressure on temperature was obtained for tds(2,4-pentanedionato)ruthenium(lll), Ru(aa)3, and tris(1,1,l-trifluoropentane-2,4-dionato)ruthenium(IlI), Ru(tfa)3. The thermodynamic characteristics of vaporization and sublimation of these complexes were determined. The processes of thermal decomposition of the vapour of the compounds in vacuum, hydrogen and oxygen were investigated by using mass spectrometry in the temperature range 170-550~ for Ru(aa)3 and 150--620~ for Ru(tfa)3. The threshold temperatures of the stability of the vapour of the complexes and the rate constants of the thermolysis processes were determined. The main gaseous products of the thermal decomposition and the dependences of their composition on the presence of hydrogen and oxygen were established.

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Dibenzylideneacetone Complexes of Transition Metals

Cited by 13 publications

References 103 publications

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

A Remarkable cis‐ and trans‐Spanning Dibenzylidene Acetone Diphosphine Chelating Ligand (dbaphos)

Formation of palladium phosphides in the reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus

Investigation of thermal properties of ruthenium(III) Β-diketonate precursors for preparation of RuO2 films by CVD

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