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Reactivity of [PdCl2(bdtp)] (bdtp – 1,5-bis(3,5-dimethyl-l- pyrazolyl)-3-thiapentane) with neutral and anionic ligands

The complex [PdCl2(bdtp)], in presence of AgBF4 orNaBF4, reacts with triphenylphosphine, pyridine, cyanide, th iocyanate and azide ligands, leading to the formation of complexes cis-[Pd(bdtp)(PPh 3)2](BF4)2 [1](BF4) 2, [Pd(bdtp)(py)2](BF4)2 [21(BF 4)2. [Pd(bdtp)(py)l(BF4)2 [3](BF4)2. [Pd(CN)2(bdtp)] [4]. and [Pd(X)(bdtp)](BF4) (X = SCN- [5](BF4), N 3- [6](BF4)). However,the similar reaction of [PdCl2(bdtp)] with AgBF4 or NaBF4 in presence of bipyridine, produces the displacement of the bdtp ligand yielding [PdCl 2(bpy)] complex. In this c ase a new synthetic route was then tried. Complex [Pd(bpy)2](BF4)2 reacts with bdtp ligand, to obtain [Pd(bpy)(bdtp)](BF4)2 [7](BF 4)2 complex. These complexes were characterised by elemental analysis, mass spectrometry, conductivity measurements, infrared and NMR spectroscopies.

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

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Cis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II)

Reactions of the platinum complexes cis-[PtCl2(PPh 3)2], [PtCl2(dppf)], or [PtCl 2(dppe)], and the palladium complexes, [PdCl2(PPh 3)2] or [PdCl2(dppe)], with bis(cyanomethyl)sulfone NCCH2SO2CH2CN in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3-dioxide complexes [M{CH(CN)SO2CH(CN)}L 2] (M = Pd, Pt) in good yields and purities. 1H and 31P{1H} NMR spectroscopy indicates that (in the majority of cases) the products are formed as a mixture of cis and trans isomers, with regard to the disposition of the cyano groups across the four-membered ring. An X-ray structure determination on a crystal of [Pd{CH(CN)SO2CH(CN)} (PPh3)2] showed it to be of the cis isomer, the first structurally characterized cis isomer of this type of complex. The four-membered palladacyclic ring is highly planar, in contrast to other metallathietane-3,3- dioxide complexes that have puckered rings. Factors influencing the relative abundances of the two isomers of [Pd{CH(CN)SO2CH(CN)}(PR 3)2] have been investigated by means of NMR spectroscopy and DFT calculations.

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

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Palladium(II)complexes of ambidentate and potentially cyclometalating 5-aryl-3-(2?-pyridyl)-1,2,4-triazine ligands

The 5-aryl-3-(2?-pyridiyl)-1,2,4-triazine ligands under study [5-phenyl-(PyTZPh)L1 5-(3-methoxyphenyl)-(PyTZ3Me-OPh)L2 5-(4-methoxyphenyl)-(PyTZ4MeOPh)L3 5-(4-trifluoromethylphenyl)-(PyTZ4CF3Ph)L4 5-(4-fluorophenyl)-(PyTZ4FPh)L5 and tris-3,5,6-(2?-pyridyl)-1,2,4-triazine (Py3TZ)L6] react with [(COD)PdCl2] (COD = 1,5-cyclooctadiento form complexes [(L1-6)PdCl2] with N,N bidentate binding ligands, also including the potentially N,N,N tridentate ligand L6. This was concluded from an in-depth NMR spectroscopic study of the new complexes and from comparison with Pd-terpy complexes [(R? terpy)PdCl]Cl [R?terpy = 4?-R?-2,2?:6?,2??-terpyridine R? = H or SMe], showing definite tridentate N,N,N coordination, and with the Pd-bpy complexes [(bpy)Pd(Mes)Cl] and [(bpy)PdCl2], show-ing definite bidentate N,N binding. The new ligands and complexes were fully characterised by multinuclear NMR spectroscopy, IR spectroscopy and mass spectrometry. No evidence for the parent triazine complexes is observed in EI-MS instead, cyclometalated complexes (HCl eliminatiowere detected in all cases. TDA/TG experiments support this assumption. Attempts to prepare the cyclometalated derivatives as substances failed, in line with the unfavourable binding mode. Detailed electrochemical measurements reveal ligand-centred reductions at very moderate potentials, in line with UV/Vis absorption spectroscopy and DFT calculations, revealing very low-lying triazine-centred LUMOs. Results from cyclic voltammetry also support the composition of [(Py3TZ)PdCl2].

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

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Coordination modes of 2-mercaptonicotinic acid: Synthesis and crystal structures of palladium(II), platinum(II), rhenium(III) and molybdenum(VI) complexes

New Pd(II), Pt(II), Re(III), Mo(VI) and Mo(V) complexes with 2-mercaptonicotinic acid (HnicSH), [Pd(PPh3)(HnicS)2]¡¤0.5CH3OH 1, [Pd(HnicS)2]¡¤CH3OH 2, [Pt(PPh3)(HnicS)2]¡¤NEt3¡¤ H2O 3, [Pt(HnicS)2] 4, [Pt(bipy)(HnicS)2]¡¤CH3OH 5, [Re(PPh3)(OCH3)(HnicS)2] 6, [ReI2(PPh3)2(HnicS)] 7, [MoO2(CH3NicS)2] 8 and [Mo2O3(CH3nicS)4]¡¤DMF 9 have been prepared. The crystal structures of compounds 1, 3, 8 and [ReI2(PPh3)2(HnicS)]¡¤0.5H2 O¡¤DMF (7¡¤0.5H2O¡¤DMF) were determined by X-ray diffraction. Complexes 1 and 3 contain two HnicS- ligands bonded in two different coordination modes: monodentate (S) and chelating (N,S). Complexes 7 and 8 contain only one HnicS- ligand which is bidentate (N,S). Infrared, 1H and 13C-{1H} NMR spectroscopic data for the complexes are presented. The Mo(VI) complex 8 is active towards oxygen atom transfer reactions and can catalyse the oxidation of benzoin and PPh3 with dmso; the catalysis occurs via the Mo(V) complex 9 which has been isolated and characterized.

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

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Synthesis and characterization of Pd(II) and Pt(II) complexes with triazolopyrimidine derivatives: The crystal structure of [Pd2L2Cl4] where L = 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

The Pd(II) and Pt(II) complexes with triazolopyrimidine C-nucleosides L1 (5,7-dimethyl-3-(2?,3?,5?-tri-O-benzoyl-beta-d-ribofuranosyl-s-triazolo)[4,3-a]pyrimidine), L2 (5,7-dimethyl-3-beta-d-ribofuranosyl-s-triazolo[4,3-a]pyrimidine) and L3 (5,7-dimethyl[1,5-a]-s-triazolopyrimidine), [Pd(en)(L1)](NO3)2, [Pd(bpy)(L1)](NO3)2, cis-Pd(L3)2Cl2, [Pd2(L3)2Cl4] ¡¤ H2O, cis-Pd(L2)2Cl2 and [Pt3(L1)2Cl6] were synthesized and characterized by elemental analysis and NMR spectroscopy. The structure of the [Pd2(L3)2Cl4] ¡¤ H2O complex was established by X-ray crystallography. The two L3 ligands are found in a head to tail orientation, with a Pd?Pd distance of 3.1254(17) A?. L1 coordinates to Pd(II) through N8 and N1 forming polymeric structures. L2 coordinates to Pd(II) through N8 in acidic solutions (0.1 M HCl) forming complexes of cis-geometry. The Pd(II) coordination to L2 does not affect the sugar conformation probably due to the high stability of the C-C glycoside bond.

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

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Perfluoroalkylation of Square-Planar Transition Metal Complexes: A Strategy to Assemble Them into Solid State Materials with a pi-pi Stacked Lamellar Structure

Formation of pi-pi stacked lamellar structure is important for high performance organic semiconductor materials. We previously demonstrated that perfluoroalkylation of aromatics and heteroaromatics was one of the strategies to design organic crystalline materials with pi-pi stacked lamellar structures while improving air stability as a result of the strong electron withdrawing ability of perfluoroalkyl substituents. Square-planar transition metal complexes with large pi-conjugated ligands are also an important category of semiconductor materials. We have perfluoroalkylated square-planar transition metal complexes, leading to the formation of a pi-pi stacked lamellar crystal packing motif in the solid state. Here we report six crystal structures of Pd and Pt complexes with bis-perfluorobutylated catechol ligand as one of the two ligands that bonds to the metal centers. This structural design possesses similar molecular topology when compared to perfluoroalkylated aromatics and heteroaromatics we have reported previously, again, demonstrating the steering power of the perfluoroalkyl substituents in engineering organic and organometallic solid state materials.

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

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In situ generated cationic Pd(II)/bipyridine-catalyzed addition of arylboronic acids to N-sulfonyl-arylaldimines

An in situ generated cationic Pd(II)/bipyridine-catalyzed nucleophilic addition of arylboronic acids to N-sulfonyl arylaldimines was developed and optimized, and the reaction was proceeded highly efficiently and conveniently in CH3NO2. A series of arylboronic acids and N-sulfonyl arylaldimines were surveyed, and 12 of 13 examples gave 90?96% yields.

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

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(2,4,6-tris(trifluoromethyl)phenyl)palladium(II) complexes

Complexes containing one or two Fmes ligands (Fmes = 2,4,6-tris(trifluoromethyl)phenyl = nonafluoromesityl) either trans or cis are obtained by treating palladium(II) chloro complexes with Li(Fmes): trans-[PdCl2L2] (L = tetrahydrothiophene (tht), PPh3) lead to trans[Pd(Fmes)ClL2] (L = tht, PPh3) or trans-[Pd(Fmes)2L2] (L = tht); [PdCl2(L-L)] (L-L = 1,5-cyclooctadiene, 2,2?-bipyridine) give [Pd(Fmes)Cl(L-L)} (L-L = COD, bipy) or [Pd(Fmes)2-(bipy)]. The structures of two complexes containing two Fmes ligands in trans and cis arrangement, trans-[Pd(Fmes)2(tht)2] (2) and [Pd(Fmes)2(bipy)] (6), respectively, have been determined by X-ray diffraction. In spite of the severe steric congestion the complexes are four coordinated. Distortions due to the bulkiness of the ortho substituents and short Pd…F3C-ortho distances are observed. The high degree of steric crowding is also responsible for slow rotation around the Pd-P bonds in the complex trans-[Pd(Fmes)Cl(PPh3)2]. DeltaG? associated with this motion is 12.8 kcal mol-1, one of the highest values reported so far for rotation around M-PPh3 bonds. Complexes 2 and 6 are redox inactive by cyclic voltammetry in the range -1.8 to +1.8 V.

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

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Water-promoted palladium catalysts for methane oxidation

A water-tolerant, active and high-selective palladium catalyst, (2,2?-bipyridine) dichloropalladium(II) is proposed for the oxidation of methane to a methanol derivative with molecular oxygen as the oxidant at temperatures below 120 C, and its activity can be increased by three times at 100 C when the volume ratio of water to CF3COOH solvent is 1:5. In addition, the addition of perfluorooctane can enhance the yield of methanol further.

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

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Di- and tripalladium(II) and -platinum(II) complexes containing 7-amino- 1,8-naphthyridin-2-one as a bridging ligand – Oxidation of a [Pt3]6+ core to [Pt3]8+

All three dinuclear complexes [Pd2(donp)2(bpy)2] (1) (H2donp = 1,8- naphthyridin-2,7-dione), [Pd2(H2nonp)2(bpy)2](ClO4)2 (2), and [Pt2(H2nonp)2(bpy)2](PF6)2 (3) (H3nonp = 7-amino-1,8-naphthyridin-2- one) exhibit the mu-1kappaN1:2kappaN8 bridging mode for their head/tail orientated naphthyridine ligands. Whereas 1 and 3 may be prepared by direct reaction of the dinucleating ligand with [MCl2(bpy)], formation of competing tripalladium(II) complexes must be avoided for 2 by employment of the precursor H2acnonp (7-acetamido-1,8-naphthyridin-2-one), which affords [H2nonp]- on cleavage of its original acetyl group. A mixture of the head/tail (4a) and head/head (4b) isomers of [Pd3(Hnonp)2(bpy)3](ClO4)2 is obtained when H3nonp is treated with [PdCl2(bpy)] and LiOH at room temperature for 2 d, followed by precipitation with LiClO4. Contrastingly exclusive formation of 4a is observed upon refluxing this reaction mixture for 3 d in aqueous solution. The [Hnonp]2- ligands exhibit a mu3- 1kappaN1:2kappaN8:3kappaN7 bridging mode that leads to short Pd ¡¤¡¤¡¤ Pd interactions of 2.781(2) and 2.775(2) A. Similar metal-metal distances of 2.771(3) and 2.816(3) A are observed in head/head- [Pt3(acnonp)(Hnonp)(bpy)3]Cl2 (5). An in situ 2e–oxidation (Ag+/Ag) of the [Pt3]6+ core in triplatinum(II) species such as 5 formed by the reaction of [PtCl2(bpy)] with H2acnonp allows the isolation of diamagnetic dark-brown head/head-[Pt3(Hnonp)2(NO3)(bpy)3](ClO4)2 (NO3) (6) with an average oxidation state of Pt (2.67+). The Pt-Pt distances of 2.723(2) and 2.670(2) A are markedly shorter than in 5.

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