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The reaction of [Pd(dtbpf)Cl2] (dtbpf = 1,1?-bis(di-tert- butylphosphino)ferrocene) with a chemical oxidant led unexpectedly to the formation of [Pd(dtbpf)Cl]+. Further study found that a variety of reagents could be used to abstract a chloride ligand from [Pd(dtbpf)Cl 2] to yield [Pd(dtbpf)Cl]+. The solid-state structure suggests the formation of an Fe-Pd interaction. The presence of the bulky tert-butyl groups is essential, as similar reactions with [Pd(PP)Cl2] (PP = other 1,1?-bis(phosphino)ferrocene ligands) results in the formation of [Pd(PP)(mu-Cl)]22+. The analogous platinum compounds have also been investigated and appear to behave in a similar manner. Similar compounds of the type [M?(PP)(PR3)]2+ (M? = Pd, Pt, R = Ph, Me) have been prepared, and a metal-metal interaction has also been observed. Steric and electronic effects dictate the formation of these compounds. X-ray crystal structures were obtained for eight of these compounds and were used as the basis for a computational analysis of the metal-metal interaction. DFT analysis indicates the presence of a weak, noncovalent interaction between the two metal centers. The electrochemical properties of these compounds were examined by cyclic voltammetry and typically show one oxidative wave and either one two-electron or two one-electron reductive waves.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Oxidative carbonylation of alkynes can be carried out catalytically in the absence of added oxidants if it is coupled with a reductive carbonylation process at the expense of the same alkyne involved in the oxidative process.Maleic esters (from oxidative carbonylation) and unsaturated lactones (from reductive carbonylation) are the main products formed under the catalytic action of palladium iodide complexes with thiourea (tu).A complex, formally corresponding to the ionic formula I, allows the reaction of alkylacetylenes at room temperature and atmospheric pressure.With activated alkynes such as phenylacetylene, or with alkynes containing coordinating groups, other palladium complexes with two or four molecules of thiourea are also active, although to a lesser extent.Identification of the organic by-products gives a hint of the mechanism by which coupling of oxidative and reductive carbonylation occurs.Keywords: Palladium; Alkynes; Oxidative carbonylation; Reductive carbonylation; Catalysis, Thiourea

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The trans-chelating ligand 1,2-bis(2?-pyridylethynyl)benzene (1) was prepared in a single step by a Sonogashira cross-coupling reaction. Treatment of 1 with trans-bis-(acetonitrile)palladium chloride provides the complex [Pd-(1)Cl2] while treatment with tetrakis(acetonitrile)palladium-(II) tetrafluoroborate provides the 2:1 complex [Pd(1)2](BF4]2. The structural, spectroscopic, and thermal properties of 1 and its Pd(II) complexes are examined.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The alternating copolymerization of 3,3-dimethylallene with carbon monoxide was achieved using [Pd(PPh3)2(MeCN)2](BF4)2 as the catalyst. The use of bidentate phosphines resulted in drastically reduced yields. In order to gain insight into the copolymerization mechanism, the stepwise successive insertions of 3,3-dimethylallene and carbon monoxide into palladium-carbon bonds in the complexes, Pd(PPh3)2(Me)(Cl), [Pd(PPh3)2(C(O)-C6H4-Me-p)(MeCN)](BF4), and [Pd[(Dppp)(Me)(MeCN)](BF4) (Dppp: 1,3-bis(diphenylphosphino)propane), were studied. These studies, in turn, led to a novel living catalytic system which was used to synthesize a terpolymer with alt-allene-carbon monoxide and alt-ethene-carbon monoxide blocks.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Phenolic compounds can be prepared by catalytic decarboxylation of 4-hydroxybenzoic acid or desulfonation of 4-hydorxybenzene sulfonic acid. Palladium complexes are shown to be highly active in the decarboxylation reaction, but complexes of platinum or ruthenium also show some activity in this reaction. Highly electron donating diphosphines such as BDTBPMB or monophosphines such as PtBu3 were found to be more effective than the less donating dppe or PPh3. The addition of D 2O led to deuteration of the aromatic ring mainly in the position ortho to the hydroxyl group. Phenol can also be generated by SO3 extrusion from 4-hydroxybenzenesulfonic acid catalysed by highly electron rich palladium complexes. The Royal Society of Chemistry 2009.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Fullerenes and their derivatives are of tremendous technological relevance. Synthetic access and application are still hampered by tedious purification protocols, peculiar solubility, and limited control over regioselective derivatization. We present a modular self-assembly system based on a new low-molecular-weight binding motif, appended by two palladium(II)-coordinating units of different steric demands, to either form a [Pd2L14]4+ cage or an unprecedented [Pd2L23(MeCN)2]4+ bowl (with L1 = pyridyl, L2 = quinolinyl donors). The former was used as a selective induced-fit receptor for C60. The latter, owing to its more open structure, also allows binding of C70 and fullerene derivatives. By exposing only a fraction of the bound guests’ surface, the bowl acts as fullerene protecting group to control functionalization, as demonstrated by exclusive monoaddition of anthracene. In a hierarchical manner, sterically low-demanding dicarboxylates were found to bridge pairs of bowls into pill-shaped dimers, able to host two fullerenes. The hosts allow transferring bound fullerenes into a variety of organic solvents, extending the scope of possible derivatization and processing methodologies.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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(Figure Presented) We report the synthesis of several unique, boron-rich pincer complexes derived from mcarborane. The SeBSe and SBS pincer ligands can be synthesized via two independent synthetic routes and are metalated with Pd(II). These structures represent unique coordinating motifs, each with a Pd?B(2) bond chelated by two thio- or selenoether ligands. This class of structures serves as the first example of boron?metal pincer complexes and possesses several interesting electronic properties imposed by the m-carborane cage. Copyright

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A new method is described for palladium-catalyzed allylic silylation using allylic alcohols and disilanes as precursors. The reactions proceed smoothly under mild and neutral conditions, and this method is suitable for synthesis of regioand stereodefined allylsilanes. The presented silylation reaction can be easily extended to include synthesis of allylboronates by change of the dimetallic reagent. The presented synthetic procedure offers a broad platform for the selective synthesis of functionalized allyl metal reagents, which are useful precursors in advanced organic chemistry and natural product synthesis.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The preparation of an 1,3-alternate calix[4]arene phosphorus ligand, 25,27-bis(2-(diphenylphosphino)ethoxy)-26,28-bis(1-propyloxy)calix[4]arene (3), is presented. Ligand 3 is obtained in three steps in 64% overall yield. Reaction of 3 with [Rh(cot)2]BF4 produced the encapsulated rhodium complex [Rh{(P,P)-diphen-calix[4]arene}]BF4 (4). As revealed by a single-crystal X-ray diffraction study, the rhodium center has a bent coordination environment with a P-Rh-P angle of 135.66(3). Palladation of 3 employing [Pd(MeCN)4](BF4)2 yielded the chelate palladium complex 7 in which the palladium center has a slightly bent configuration. Treatment of the ligand with Pd(cod)Cl2 and [Pd(eta3-C4H7)(THF)2]BF 4 leads to the isolation of the monometallic complex. Full characterization includes X-ray structural studies of compounds 3, 4, and 6.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Readily synthesised and functionalised di-1,4-substituted-1,2,3-triazole “click” ligands are shown to self-assemble into coordinatively saturated, quadruply stranded helicate molecular cages with Pd(ii) ions.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method