(η
            <sup>3</sup>
            ‐Allyl)Palladium(II) Complexes

Tatsuno, Yoshitaka; Yoshida, Tomohiro; Seiotsuka,; Al-Salem, Najeeb A.; Shaw, Bernard L.

doi:10.1002/9780470132500.ch51

Cited by 184 publications

(50 citation statements)

References 4 publications

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“…The starting materials were obtained either from Aldrich or Alfa Aesar and were used without further purification. The following compounds were synthesized according to reported methods: [(h 5 -C 5 H 4 PPh 2 )TiCl 3 ] (6 a), [13] [(C 5 H 4 PPh 2 )Li], [12] [(C 5 H 4 PiPr 2 )Li], [12] [(h 5 -C 5 H 4 PPh 2 ) 2 ZrCl 2 ] (7 a), [12] [(h 5 -C 5 H 4 PiPr 2 ) 2 ZrCl 2 ] ( 7 b), [12] [(h 5 -C 5 H 5 )PdA C H T U N G T R E N N U N G (h 3 -C 3 H 5 )], [40] and [{(cod)RhCl} 2 ]. [41] [(h 5 -C 5 H 4 PiPr 2 )TiCl 3 ] (6b): C 5 H 4 A C H T U N G T R E N N U N G (SiMe 3 )PiPr 2 was prepared in an analogous manner to that described for C 5 H 4 A C H T U N G T R E N N U N G (SiMe 3 )PPh 2 .…”

Section: Methodsmentioning

confidence: 99%

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Büschel

Jungton

Bannenberg

et al. 2009

Chemistry A European J

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Twice as reactive: The coordination chemistry of phosphane-functionalized Zr and Hf cycloheptatrienyl-cyclopentadienyl complexes gives rise to unusual secondary interactions associated with the presence of Lewis acidic 16-electron sandwich moieties. These structures can develop weak dative bonds as exemplified by the noncovalent Pd-->Zr interaction in the heterobimetallic {Zr(2)Pd} complex (see picture). Phosphane-functionalized cycloheptatrienyl-cyclopentadienyl Group 4 metal complexes of the type [(eta(7)-C(7)H(7))M(eta(5)-C(5)H(4)PR(2))] (M=Ti (9); M=Zr (10); M=Hf (11); R=Ph (a); R=iPr (b)) have been prepared by the reduction of [(eta(5)-C(5)H(4)PR(2))TiCl(3)] or [(eta(5)-C(5)H(4)PR(2))(2)MCl(2)] (M=Zr, Hf) with magnesium in the presence of cycloheptatriene (C(7)H(8)). In the solid state, the Ti complex 9 a and the complex 11 b are monomeric, whereas 10 a, 10 b, and 11 a form dimers, in which the sandwich units are linked by long Zr-P or Hf-P bonds. Density-functional theory (DFT) calculations indicate that the metal-phosphane interaction is weak, and accordingly, both the Ti complex 9 b and the Zr complex 10 b act as monodentate phosphane ligands upon reaction with [{(cod)RhCl}(2)] (cod=eta(4)-1,5-cyclooctadiene). The X-ray crystal structures of [(cod)Rh(9 b)Cl] (12) and [(cod)Rh(10 b)Cl] (13) reveal that only the latter exhibits a secondary intramolecular Cl-metal interaction. The complex [(10 b)(2)Pd] (14) was obtained by reaction of [(eta(5)-C(5)H(5))Pd(eta(3)-C(3)H(5))] with two equivalents of 10 b. The solid-state structure of 14 reveals a T-shaped Pd(0) center with a long Pd-Zr bond of 2.9709(3) A, which can be interpreted as a weak noncovalent Pd(0)-->Zr(+IV) bond, as indicated by the calculated relaxed force constant of 5.68 N m(-1).

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Section: Methodsmentioning

confidence: 99%

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Büschel

Jungton

Bannenberg

et al. 2009

Chemistry A European J

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“…[16] Allylpalladium(II)chloride dimer (2.5 g) was dissolved in absolute THF (50 mL) and cooled to À60 8C. Drop wise addition of NaCp (6 mL, Cp = cyclopentadienyl) under constant cooling and stirring lead to a red coloring of the solution, which was stirred for another 15 min at À20 8C and for 30 min at RT.…”

Section: Starting Materials Synthesismentioning

confidence: 99%

Selective Palladium‐Loaded MIL‐101 Catalysts

Hermannsdörfer

Kempe

2011

Chemistry A European J

126

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Palladium nanoparticles (NPs) of different mean particle size have been synthesized in the host structure of the porous coordination polymer (or metal-organic framework: MOF) MIL-101. The metal-organic chemical vapor deposition method was used to load MIL-101 with the Pd precursor complex [(η(5)-C(5)H(5))Pd(η(3)-C(3)H(5))]. Loadings higher than 50 wt.% could be accomplished. Reduction of the Pd precursor complex with H(2) gave rise to Pd NPs inside the MIL-101 (Pd@MIL-101). The reduction conditions, especially the temperature, allows us to make size-conform (size of the Pd NPs correlates with the size of the cavities of the host structure of MIL-101) and undersized Pd NPs. The Pd@MIL-101 samples were characterized by X-ray diffraction, IR spectroscopy, Brauner-Emmett-Teller (BET) analysis, elemental analysis, and transmission electron microscopy (TEM). Catalytic studies, hydrogenation of ketones, were performed with selected Pd@MIL-101 catalysts. Activity, selectivity, and recyclability of the catalyst family are discussed.

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“…Solvents were purified using basic alumina columns after degassing. 1,3-Bis[(diphenylphosphino)-methyl]benzene [85] and [(allyl)PdCl] 2 [86] were synthesized according to literature procedures. Morpholine and decane were distilled from CaH 2 ; cinnamyl acetate was degassed and stored over molecular sieves.…”

Section: Methodsmentioning

confidence: 99%

Molecular‐Weight‐Enlarged Multiple‐Pincer Ligands: Synthesis and Application in Palladium‐Catalyzed Allylic Substitution Reactions

et al. 2009

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Three different pincer ligand systems are synthesized via nucleophilic substitution reactions of polyaromatic benzyl bromides as support molecules and phenol derivatives as ligand precursors. Retention tests using a polymeric nanofiltration membrane show moderate to good retention in THF and CH(2)Cl(2). Concentration-dependent NMR spectroscopy gives no indication for the formation of aggregates in solution. The three ligand systems are active in both the allylic alkylation and allylic amination reactions and show high selectivity towards the linear trans products. An investigation of the kinetic parameters of the allylic amination reaction show that the reaction of cinnamyl acetate with morpholine is of zero order in cinnamyl acetate and of first order in morpholine. The order in catalyst is found to be one, and the rate constant k' is determined for a reaction under standard conditions. Moreover, one of the tri(pincer)-palladium complexes is used as soluble, molecular-weight-enlarged homogeneous catalyst in continuous allylic alkylation and amination reactions. The conversion of the allylic alkylation reaches a maximum of 30 %, while a maximum conversion of 80 % is reached in the allylic amination reaction. No palladium black was formed.

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(η ³ ‐Allyl)Palladium(II) Complexes

Cited by 184 publications

References 4 publications

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Selective Palladium‐Loaded MIL‐101 Catalysts

Molecular‐Weight‐Enlarged Multiple‐Pincer Ligands: Synthesis and Application in Palladium‐Catalyzed Allylic Substitution Reactions

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(η 3 ‐Allyl)Palladium(II) Complexes

Cited by 184 publications

References 4 publications

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Selective Palladium‐Loaded MIL‐101 Catalysts

Molecular‐Weight‐Enlarged Multiple‐Pincer Ligands: Synthesis and Application in Palladium‐Catalyzed Allylic Substitution Reactions

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(η ³ ‐Allyl)Palladium(II) Complexes