Divergent Route to Organoplatinum or Platinum−Palladium Dendrimers

Liu, Guoxing; Puddephatt, Richard J.

doi:10.1021/om960716w

Cited by 39 publications

(26 citation statements)

References 15 publications

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“…The reactor was flushed with 10 reactor volumes and the amounts of palladium and phosphorus on both sides of the membrane were determined by ICP-AES. The retention of 13-[Pd(allyl)Cl] 12 was 99.7%, indicating that the catalyst, which was in the Pd II state, was stable under these conditions. During the catalytic cycle the catalyst also becomes Pd 0 , and so we attempted a retention measurement of the catalyst in the Pd 0 state.…”

Section: Continuous Processmentioning

confidence: 98%

“…[63] The two doublets in the 31 P{ 1 H} NMR spectrum of 12-(PdMeCl) 4 (at δ ϭ 31.3 and 2.75; J ϭ 39.0 Hz) clearly showed the coupling of the inequivalent phosphorus atoms. For 13-(PdMeCl) 12 the coupling between these atoms could not be observed, because the signals had broadened significantly. However, the two signals found in the 31 P{ 1 H} NMR spectrum at δ ϭ 30.8 and 2.38 suggested that cis complexes were formed.…”

Section: Formation Of the Palladium Complexesmentioning

confidence: 99%

“…Turnover numbers of over 15,000 were reached in the batch process with 13-[Pd(allyl)Cl] 12 , indicating that this is a stable dendrimeric catalyst that might perform very well in a continuous process if a membrane reactor was used.…”

Section: Batch Processmentioning

confidence: 99%

“…For the continuous process, a solution of allyl trifluoroacetate and sodium diethyl 2-methylmalonate in THF (with n-decane as an internal standard) was pumped through the reactor and 13-[Pd(allyl)Cl] 12 was used as a catalyst.…”

Section: Continuous Processmentioning

confidence: 99%

“…To study other possible deactivation pathways, we explored the stability of the 13-[Pd(allyl)Cl)] 12 catalyst system by performing retention measurements in dichloromethane. The reactor was flushed with 10 reactor volumes and the amounts of palladium and phosphorus on both sides of the membrane were determined by ICP-AES.…”

Section: Continuous Processmentioning

confidence: 99%

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Palladium Complexes of Phosphane-Functionalised Carbosilane Dendrimers as Catalysts in a Continuous-Flow Membrane Reactor

et al. 2002

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Phosphane‐functionalised carbosilane dendrimers 9, 10, 11, 12, 13, 19 and 20 have been synthesised, and their palladium complexes have been used as catalysts in the allylic substitution reaction. The catalytic sites at the periphery of the dendrimer support are readily accessible to the substrate, which is reflected − also for the larger dendrimeric systems − in the high catalytic activity. Moreover, the higher generations are sufficiently large to be retained by a nanofilter, and dendrimeric catalysts 13 and 20 have been applied in a continuous‐flow membrane reactor. The stability of the palladium complexes of the phosphane‐functionalised dendrimers is crucial for application in a continuous process of this type, and appeared to be very sensitive to small changes in the dendrimeric structure. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Continuous Processmentioning

confidence: 98%

Section: Formation Of the Palladium Complexesmentioning

confidence: 99%

Section: Batch Processmentioning

confidence: 99%

Section: Continuous Processmentioning

confidence: 99%

Section: Continuous Processmentioning

confidence: 99%

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Palladium Complexes of Phosphane-Functionalised Carbosilane Dendrimers as Catalysts in a Continuous-Flow Membrane Reactor

et al. 2002

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Metal‐Containing Polymers

Abd‐El‐Aziz¹

2002

Encyclopedia of Polymer Science and Technology

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The focus of this article is on the synthesis, properties, and applications of metal‐containing polymers. These polymers may be classified based on the types of metal–ligand bonding, and whether the metal is an integral part of the polymer backbone or pendent to the polymer backbone. The first class of polymers discussed are those with metals σ‐bonded to organic spacers in their backbones. Examples of metal–metal single and multiple bonds are also described. Metallocenes and coordination polymers are two classes of polymers where the metal is π‐coordinated to the organic ligands. The coordination of metals to porphyrins, phthalocyanines, Schiff base ligands, as well as to many other types of ligands are described. Another major class of polymers are those where the metal is pendent to the polymer backbone. These polymers include materials with metallic moieties π‐coordinated to unsaturated ligands in their backbones. Polymers with metallic moieties in their side chains are also described. A brief overview of star polymers and dendrimers is also included.

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Formation of Metallamacrocycles from Palladium(II), Platinum(II) and Copper(I) Complexes and the Ditopic Ligands [{p-(Ph2PO)C6H4}2CMe2], [{2-Ph2PO-3,5-(Me3C)2C6H2}2S], [{p-[(C10H6O)2PO]C6H4}2CMe2]

Arena

Drommi

Faraone

et al. 2001

Eur. J. Inorg. Chem.

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The new ligands bis(phosphinito) [{2-Ph 2 PO-3,5-(Me 3 C) 2 C 6 H 2 } 2 S] (4) and chiral bis(phosphite) [{p-[(C 10 H 6 O) 2 PO]C 6 H 4 } 2 CMe 2 ] (5) were synthesised and their reactions with palladium(II), platinum(II), copper(I) substrates were studied. The ligand 3 [{p-(Ph 2 PO)C 6 H 4 } 2 CMe 2 ], previously reported by us, was also used in the same reactions. Ligands 3 and 5 formed 28-membered metallamacrocycles while ligand 4 afforded the analogous compound only in the reaction with the copper(I) substrate. In the reaction of 3 with [Pd(PhCN) 2 Cl 2 ] the metallamacrocycle [PdCl 2 (µ-3)] 2 (6) or the oligomer [Pd 2 Cl 4 (µ-3)] n (7) were formed, depending on the molar ratio used. The reaction of 3 with [Pd(η 3 -C 3 H 5 )Cl] 2 afforded compound {[Pd(η 3 -C 3 H 5 )Cl] 2 (µ-3)} (8). The allylpalladium macrocycle [Pd(η 3 -C 3 H 5 )(µ-3)] 2 [OTf] 2 (9) was obtained by treating a solution of 8 in THF with [a]

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Divergent Route to Organoplatinum or Platinum−Palladium Dendrimers

Abstract: A new divergent route to organotransition-metal dendrimers is described, in which a key step involves oxidative addition. The product dendrimers contain organoplatinum(IV) centers in each inner generational layer and either platinum(II) or palladium(II) centers in the outermost layer.

Cited by 39 publications

References 15 publications

Palladium Complexes of Phosphane-Functionalised Carbosilane Dendrimers as Catalysts in a Continuous-Flow Membrane Reactor

Palladium Complexes of Phosphane-Functionalised Carbosilane Dendrimers as Catalysts in a Continuous-Flow Membrane Reactor

Metal‐Containing Polymers

Formation of Metallamacrocycles from Palladium(II), Platinum(II) and Copper(I) Complexes and the Ditopic Ligands [{p-(Ph2PO)C6H4}2CMe2], [{2-Ph2PO-3,5-(Me3C)2C6H2}2S], [{p-[(C10H6O)2PO]C6H4}2CMe2]

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