0000000000026400
AUTHOR
Bruno Crociani
Preparation and reactions of palladium(II) complexes with C2-bonded heteroaromatic ligands trans[PdCl(RN)(PPh3)2] (RN = 2-pyridyl, 2-pirazyl, 2-pyrimidyl group). A new reaction pathway in the insertion of isocyanides into the Pdc bond of trans-[PdXR(L)2] compounds
Abstract The complexes trans -[PdCl(R N )(PPh 3 ) 2 ] (I) [R N = 2-pyridyl (2-Py), 2-pyrazyl (2-pyz), 2-pyrimidyl (2-pym) group] have been prepared in high yield by deprotonation with NEt 3 of the corresponding cationic compounds trans [PdCl(R N H) (PPh 3 ) 2 ] + (R N H = N -protonated C 2 -heteroaromatic ligand) in the presence of an excess of PPh 3 . In chlorinated solvents, complexes I undergo a slow reversible dimerization into the binuclear derivatives [PdCl(μ-R N )(PPh 3 )] 2 (II) (μ-R N = C 2 , N 1 -bridging ligand). From the 31 P NMR spectra in 1,2-dichloroethane the following dissociation constants were obtained: 1.9 mol 1 −1 (R N = 2-py), 5.1 × 10 −2 (2-pym), 6.6 × 10 −3 (2-pyz). …
Reactions of α-diimino ligands with the chloro-bridged dimer [RhCl(COD)]2(COD=1,5-cyclooctadiene)
Abstract The reactions of α-diimino ligands N - N ′ [ N - N ′= 2,2′-bipyridine (bipy), C 5 H 4 N2CHNR (R= C 6 H 4 OMe- p , PyCa), RNCHCHNR (R=C 6 H 4 - OMe- p , DAB)] with [RhCl(COD)] 2 give rise to stoichiometry, solvent, ligand, and temperature dependent equilibria. In general, the 1/1 ligand/dimer reaction yields the ionic product [Rh(COD)( N - N ′)] [RhCl 2 (COD)], at room temperature. For N - N ′=DAB, the ionic form is in equilibrium with the binuclear compound [{RhCl(COD)} (μ-DAB){RhCl(COD)}] (containing a σ σ,'- N , N ′ bridging α-diimine), which becomes the predominant species at low temperatures. In [Rh(COD)( N - N ′)] [RhCl 2 (COD)], a fast exchange of the Rh(COD) unit betwe…
Nucleophilic attack by 2-pyridylpalladium(II) and platinum(II) complexes on the organic chlorides ClCH2R (R COMe, CN, Ph, Cl)
Abstract The 2-pyridyl complexes trans-[MCl(C5H4NC2)(PPh3)2] (M = Pd, 1a; M = Pt, 1b), [MCl(C5H4NC2)(dppe)] (M = Pd, 2a; M = Pt, 2b) and [M(dmtc)(C5H4NC2) (PPh3)] (M = Pd, 3a; M = Pt,3b) react with the chlorides ClCH2R(R COMe, CN, Ph) to give cationic products containing the 2-pyridylium ligands (1-CH2R)C5H4NC2. The rate of nucleophilic displacement of the chloride ion from ClCH2R depends on the central metal (Pt > Pd), on the coordination geometry (1 ~ 3) and on the substituent R (COMe > CN > Ph for the reactions with 3b). Like 1b and 2b, complex 3b also reacts with dichloromethane to give [Pt(dmtc){(1-CH2Cl)C5H4NC2}(PPh3)]+. The reaction of the binuclear compound [{PdCl(μ-C5H4NC2,…
Theoretical and Spectroscopic Studies On Imino-carbon Palladated Pyridine-2-carbaldimines
Abstract Ab initio LCAO-MO-SCF calculations on the model compounds C 5 H 4 N-2-C(R 1 )=NH [R 1 = H ( 2c ) and R 1 = trans -PdCl(PH 3 ) 2 ( 4c )] indicate that the E - trans conformation is favored over the E - cis one by 16.9 kJ mol −1 for 2c and by 25.0 kJ mol −1 for 4c . One of the factors which stabilizes the E-trans arrangement for 4c is a weak bonding interaction between the palladium center and the pyridine nitrogen. On going from 2c to 4c a slight charge enrichment on the pyridine carbons and a more pronounced one on the nitrogen atoms is computed, whereas the charge density of the imino carbon atom is decreased. In 4c no π contribution to the PdC bond is observed. Protonation of th…
Stereo and regioselectivity in the phenylation of cationic allylpalladium(II) α-diimine complexes by tetraphenylborate anion
The reaction of the cationic complex [Pd(4-methoxy-1,3-η3-cyclohexenyl)(py-2-CHNC6H4OMe-4)]+ (1) with BPh4− in the presence of fumaronitrile yields trans-3-methoxy-6-phenylcyclohexene (2a) and trans-4-methoxy-3-phenylcyclohexene (2b), in ca. 1 : 1 molar ratio. The trans stereochemistry of these products implies that the phenylation of the allyl ligand involves prior transfer of a phenyl group from BPh4− to the metal, followed by reductive coupling of the organic moieties. In the reactions of [Pd(η3-1,1-R1,R2-C3H3)(NN′)]+ (3) [NN′ 4-MeOH4C6NCHCHNC6H4OMe-4; py-2-CHNR (R C6H4OMe-4, Me, or CMe3), 2,2′-bipyridine (bipy); R1 H, R2 Ph, Me; R1 R2 Me; with BPh4− in the presence of …
Reactions of pyridine-2-carbaldimines with chloro-bridged palladium(II) and platinum(II) 2-methylallyl dimers. Solution behaviour of the cationic complexes [M(n3-2-MeC3H4)(py-2-CHNR)]+
Abstract The reactions of pyridine-2-carbaldimines, py-2- CHNR (R = C6H4OMe-p, Me), with allylic dimers [MCl(n3-2-MeC3H4)]2 give rise to stoichiometry, concentration, solvent and temperature dependent equilibria, in which the cationic complexes [M(n3- 2-MeC3H4)(py-2-CHNR)]+ and the anion [MCl2(n3- 2-MeC3H4)]- or Cl- are involved. In general, the ligand/dimer reaction (1/1 molar ratio) yields the ionic products [M(n3-2-MeC3H4)(py-2-CHNR)]- [MCl2(n3-2-MeC3H4)], which can be isolated as solids, whereas the same reaction in a 1/0.5 molar ratio yields the species [M(n3-2-MeC3H4 )(py-2-CH NR)] Cl, which can be studied only in solution, but are easily converted into [M(n3-2-MeC3H4)(py-2-CH NR…
PREPARATION AND REACTIONS OF 2-PYRIDYLPLATINUM(II) COMPLEXES [PTCL(C5H4N-C2)(TERTIARY PHOSPHINE)2] - COMPOUNDS WITH A MARKEDLY NUCLEOPHILIC PYRIDINE NITROGEN ATOM
Abstract The 2-pyridyl complex trans -[PtCl(C 5 H 4 N- C 2 )(PPh 3 ) 2 ] (I) can be prepared in high yield by oxidative addition of 2-chloropyridine to [Pt(PPh 3 ) 4 ]. The reaction of I with 1,2-bis(diphenylphosphino)ethane yields the cis derivative [PtCl(C 4 5 H 4 N- C 2 )(dppe)] (II). In polar solvents, the latter rearranges to the binuclear cationic complex [Pt(μ-C 5 H 4 N- C 2 , N )(dppe)] 2 Cl 2 . The reaction of I with [PdCl(η 3 -2-MeC 3 H 4 )] 2 (1/0.5 molar ratio) gives the products [PtCl(μ-C 5 H 4 N- C 2 , N )(PPh 3 )] 2 (IV) and [PdCl(η 3 -2-MeC 3 H 4 )(PPh 3 )]. 31 P NMR monitoring of the reaction suggests that PPh 3 transfer occurs in a binuclear platinum/palladium intermediate…
Coordination properties of imino(2-pyridyl)methylpalladium(II) compounds. Preparation and thermal rearrangement of binuclear adducts with palladium(II) and platinum(II) chlorides
Abstract The imino(2-pyridyl)methylpalladium(II) compound py-2-C(R′)NR (R = C 6 H 4 OMe-p, R′ = trans-PdCl(PPh 3 ) 2 ) reacts with [PdCl 2 (CH 2 CHPh)] 2 , [PdCl 2 - (NCMe) 2 ], and K[PtCl 3 (CH 2 CH 2 )] to give binuclear complexes [MCl 2 {py-2- C(R′)NR}] (M = Pd, Pt), in which the α-diimino group acts as a chelating bidentate ligand. In hot 1,2-dichloroethane, these complexes undergo a PPh 3 and chloride ligand exchange at rates which depend markedly on the metal M (Pd ⪢ Pt), to yield the new derivatives [MCl(PPh 3 ){py-2-C(cis-PdCl 2 (PPh 3 ))NR}]. The ligand exchange is followed by a much slower decomposition to [MCl 2 (PPh 3 ) 2 ]. Labile intermediates of the same type, [MCl(PPh …
Solution behaviour and relative stability of the complexes [MCl2(RNCHCHNR)] and [MCl2(py-2-CHNR)] (M=Pd, Pt;R=C6H4OMe-p)
Abstract Even though the α-diimino complexes [MCl 2 (RNCHCHNR)] and [MCl 2 (py-2-CHNR)] (M=Pd, Pt;R=C 6 H 4 OMe- p ) are poorly soluble in chlorinated solvents, such as chloroform and 1,2-dichloroethane, or in acetonitrile, the electronic and 1 H NMR spectra indicate that these compounds are generally present as undissociate monomers with σ, σ′- N,N′ chelate N-ligands in dilute solutions. Only for [PdCl 2 (RNCHCHNR)], some dissociation of the α-diimine occurs in acetonitrile. In dimethylsulfoxide, where the solubility is much higher, no dissociation is observed for the pyridine-2-carbaldimine complexes [MCl 2 (py-2-CHNR)], whereas the 1,2-bis(imino) ethane derivatives [MCl 2 (RNCH…
Protonation and methylation reactions of 2-pyridyl-palladium(II) and -platinum(II) complexes
Abstract The reactions of strong acids HX and HClO4 with the 2-pyridyl complexes [PdX(μ-C5H4N-C2,N)(PPh3)]2 (X = Cl, Br), trans-[PdCl(C5H4N-C2)(PEt3)2] and [PdCl(C5H4N-C2)(dppe)] yield the N-protonated derivatives cis-[PdX2-(C5H5N-C2)(PPh3)], trans-[PdCl(C5H5N-C2)(PEt3)2]ClO4 and [PdCl-(C5H5N-C2)(dppe)]ClO4, respectively. The terminal 2-pyridyl group of trans-[PdCl(C5H4N-C2)(PEt3)2] and [PdCl(C5H4N-C2)(dppe)] also reacts with Me2SO4/NaClO4 to give trans-[PdClC5H4(l-Me)N-C2(PEt3)2]ClO4 and [PdClC5H4(l-Me)N-C2(dppe)]ClO4. Analogous N-protonation or N-methylation reactions occur with trans-[PtBr(C5H4N-C2)(L)2] (L = PEt3, PPh3). The complexes trans-[MX(C5H5N-C2)(PMe2Ph)2]ClO4 (M = Pd, X = Cl an…
Mechanism of aminocarbene formation by nucleophilic attack on isocyanide ligands in platinum(II)2-pyrazyl and 4-pyridyl complexes
Abstract The reactions of 2-pyrazyl and 4-pyridyl isocyanide complexes [Pt(CNC 6 H 11 )(C 4 H 3 N 2 - C 2 )(dppe)ClO 4 and [Pt(CNC 6 H 11 )(C 5 H 4 N- C 4 ) (dppe)]ClO 4 ( 1 ) with amines involving the formation of aminocarbene derivatives have been studied kinetically in 1,2-dichloroethane by UV—VIS techniques. The kinetics obey the simple second-order rate law rate = k 2 [ 1 ][amine]. Low activation enthalpies and highly negative activation entropies for the k 2 term are observed. A mechanism is proposed involving direct nucleophilic attack of the amine on the isocyanide carbon with concomitant proton transfer from the amine to the isocyanide nitrogen assisted by the heterocyclic nitrogen…
Comparison of hard vaporization and soft ionization techniques in the mass spectrometry of some palladium(II) and platinum(II) complexes with C-bonded heterocyclic ligands
Abstract Electron impact, fast atom bombardment and laser induced vaporization techniques are compared in the mass spectrometric behaviour of some palladium(II) and platinum(II) complexes with C-bonded heterocyclic ligands of the type trans -[MCl(R N )(PPh 3 ) 2 ] [M = Pd, R N = 2-pyridyl, 1 ; 2-pyrazyl, 2; 2-pyrimidyl, 3; M = Pt, R N = 2-pyridyl, 4 ].
Preparation and protonation of 2-pyrimidyl- and 2-pyrazylpalladium(II) complexes
Abstract The oxidative addition of 2-chloropyrimidine or 2-chloropyrazine to [Pd(PPh 3 ) 4 ] yields a mixture of trans -[PdCl(C 4 H 3 N 2 - C 2 )(PPh 3 ) 2 ] (I) and [PdCl(μ-C 4 H 3 N 2 - C 2 , N 1 )(PPh 3 (II) (C 4 H 3 N 2 = 2-pyrimidyl or 2-pyrazyl group). The mononuclear complexes I are quantitatively converted into the binuclear species II upon treatment with H 2 O 2 . The reaction of II with HCl gives the N -monoprotonated derivatives cis -[PdCl 2 (C 4 H 4 N 2 - C 2 )(PPh 3 )] (III), from which the cationic complexes trans -[PdCl(C 4 H 4 N 2 - C 2 )(L) (L = PPh 3 , IV; PMe 2 Ph, V; PEt 3 , VI) can be prepared by ligand substitution reactions. Reversible proton dissociation occurs in so…
Adducts of 1,4-diazabutadienes with group IIB metal halides
Abstract The reactions of 1,4-diazabutadienes (or α-diimines) RNC(R′)C(R″)NR, DAB, (R = p -C 6 H 4 OMe, R′ = R″ = H, DAB I ; R = p -C 6 H 4 OMe,R′ = H, R″ = Me, DAB II ; R = p -C 6 H 4 OMe, R′= R″ = Me; DAB III ; R = CMe 3 , R′ = R″ = H, DAB IV ) with MX 2 M = Zn, Cd, Hg; X = CI, Br) yield in general 1/1 adducts. These species are assigned a monomeric configuration with a σ,σ′-N,N′, chelating DAB ligand for M = Zn, Hg, whereas the CdCl 2 adducts have polymeric structures with terminal and/or bridging chlorides. In the reactions of CdCl 2 with DAB I or DAB IV polymeric species [(CdCl 2 ) 2 (DAB)] x are obtained in which all chlorides are bridging. Spectrophotometric dissociation equilib…
Coordination properties of imino(2-pyridyl)methylpalladium(II) compounds. Reactions with the chloride-bridged allyl dimers [MCl(η3-2-MeC3H4)]2 (MPd, Pt)
Abstract The imino(2-pyridyl)methylpalladium(II) compounds py-2-CR 1 NR [R 1 = trans -PdCl(PPh 3 ) 2 , R = C 6 H 4 OMe- p ( Ia ), Me ( Ib ), CMe 3 ( Ic ); R 1 = Pd(dmtc)(PPh 3 ), R = C 6 H 4 OMe- p ( Id )] react with [MCl(η 3 - 2-MeC 3 H 4 )] 2 (M = Pd, Pt) in a molar ratio 1/0.5 and in the presence of NaClO 4 to yield the binuclear cationic complexes II , [M(η 3 -2-MeC 3 H 4 )(py-2-CR 1 NR)]ClO 4 , where the α-diimino group acts as σ,σ N , N ′ chelating ligand. In the absence of NaClO 4 and with a molar ratio 1/1, the reaction leads initially to formation of a ionic intermediate A , [M(η 3 - 2-MeC 3 H 4 )(py-2-CR 1 NR)] [MCl 2 (η 3 -2-MeC 3 H 4 )], which subsequently undergoes exchange …
Phenylation of cationic allylpalladium(II) complexes by tetraphenylborate anion. A mechanistic study
Abstract The mechanism of the reaction of allyl complexes [Pd(η3-2-R′C3H4)(NN′)]+ (NN′ = α-diimine ligand) wiht BPh4− in the presence of activated olefins (ol), yielding the products [Pd(η2-ol)(NN′)] and PhCH2C(R′)CH2, has been investigated. The results are interpreted in terms of extensive association between the cationic substrate and the BPh4− anion in a tight ion-pair, followed by rate-determining phenyl transfer to the palladium center and fast reductive elimination of allylbenzene.
Migration of bidentate anionic ligands in binuclear compounds derived from 1,2-bis(imino)propyl-palladium(II) complexes
Abstract The complexes [Pd(AB){C(NR)CMeNR}(PPh3)] (I; AB = 2,4-pentanedionate, N-methylsalicylaldiminate, pyrrole-2-N-methylaldiminate; R = p-C6H4OMe) react with ‘MCl2’ (‘MCl2’ = CoCl2, NiCl2, CuCl2, ZnCl2, [PdCl2(NCMe)2], K[PtCl3(CH2CH2)]) to give either the binuclear adducts [(PPh3)(AB)Pd{C(NR)CMeNR}MCl2] (II) or the zwitterionic isomers [(PPh3)Cl2Pd{C( NR)CMeNR}M (AB)] (III) depending on the nature of the metal M and of the anionic ligand AB. The formation of products III is accounted for in terms of an intramolecular migration of ligands between the two metal centers Pd and M of the initially formed MCl2 adducts II.
Structural studies on 2-pyridyl complexes of the platinum triad metals. The crystal and molecular structure of the 2-pyridylium derivative trans-[PdCl(C5H5NC2)(PMe2Ph)2]ClO4
Abstract In solution, the complex trans -[PdCl(C 5 H 4 N C 2 )(PMe 2 Ph) 2 ] ( 1 ) is in equilibrium with a small amount of the binuclear species [{PdCl(μ-C 5 H 4 N C 2 , N )(PMe 2 Ph)} 2 ] ( 2 ), which can be isolated upon recrystallization. The compound 1 is easily N-protonated by HClO 4 to the 2-pyridylium product trans -[PdCl(C 5 H 5 N C 2 )(PMe 2 Ph) 2 ]ClO 4 ( 3 ), which crystallizes in the orthorhombic space group P2 1 2 1 2 1 , with cell parameters a =15.761(3), b =14.369(2), c =11.132(2) A and Z =4. The X-ray crystal structure analysis of 3 , using 3744 observed reflections in the refinement and resulting in a final R value of 0.0298, shows that the coordination around palladium…
Preparation and reactivity of 1,2-bis(imino)ethylpalladium(II) complexes
Abstract The 1,2-bis(imino)ethylpalladium complex, t r a n s − [ P d C I { C ( = N R ) ︹ C H = N R } ( P P h 3 ) 2 ] (R =p-C6H4OMe, DABI) can be prepared by treatment of [Pd(PPh3)4] with two equivalents of CNC6H4OMe-p followed by slow addition of HCl at −70° C. The σ-bonded 1,2-bis(imino) group can be easily monoprotonated and undergoes acid hydrolysis to give the α-aldehydoimidoyl derivative t r a n s − [ P d C I { C ( = N R ) ︹ C H = O } ( P P h 3 ) 2 ] . Condensation of the aldehydic carbonyl group with methylamine yields the product t r a n s − [ P d C I { C ( = N C 6 H 4 O M e − p ) ︹ C H = N M e } ( P P h 3 ) 2 ] , DABII, with different substituents on the N-imino atoms. Substitution …
ChemInform Abstract: Theoretical and Spectroscopic Studies on Imino-Carbon Palladated Pyridine-2-carbaldimines.
Abstract Ab initio LCAO-MO-SCF calculations on the model compounds C 5 H 4 N-2-C(R 1 )=NH [R 1 = H ( 2c ) and R 1 = trans -PdCl(PH 3 ) 2 ( 4c )] indicate that the E - trans conformation is favored over the E - cis one by 16.9 kJ mol −1 for 2c and by 25.0 kJ mol −1 for 4c . One of the factors which stabilizes the E-trans arrangement for 4c is a weak bonding interaction between the palladium center and the pyridine nitrogen. On going from 2c to 4c a slight charge enrichment on the pyridine carbons and a more pronounced one on the nitrogen atoms is computed, whereas the charge density of the imino carbon atom is decreased. In 4c no π contribution to the PdC bond is observed. Protonation of th…
Preparation and reactions of 1-methylpyrid-6-one-2-yl compounds of palladium(II) and platinum(II)
Abstract The compounds trans -[MCl{(1-Me)C 5 H 3 (6-O)N- C 2 }(L) 2 ] (M = Pd, Pt; L = PPh 3 , PMe 2 Ph), can be prepared from the reaction of the corresponding 1-methyl-6-chloro-2-pyridylium cationic complexes, trans -[MCl{(1-Me)C 5 H 3 (6-Cl)N- C 2 }(L) 2 ]ClO 4 , with a mixture of acetic acid, ethanol, and triethylamine in the molar ratio M/MeCO 2 H/EtOH/NEt 3 of 1/3/3/4. The rate is slow compared to that of the 1-methyl-2-chloropyridinium cation under similar conditions, and is markedly affected by the steric and electronic effects of the trans -MCl(L) 2 unit. The novel 1-methylpyrid-6-one-2-yl derivatives have been characterized by conventional spectroscopic techniques and by reactions…
Insertion of isocyanides into the 2-one-1-propyl—palladium(II) bond: A convenient synthetic route to C1-palladated 1-amino-3-one-1-butene compounds
Abstract Migratory insertion of isocyanides CNR (R = p -C 6 H 4 OMe, Me) into the palladium—carbon σ bond of trans -[PdCl(CH 2 COMe)(PPh 3 ) 2 ] (I) yields the 1-amino-3-one-1-butenyl complexes trans -[PdCl{C(NHR)CHCOMe}(PPh 3 ) 2 ] (IIa, R = p -C 6 H 4 OMe; IIb, R = Me), which have been characterized by IR, 1 H and 31 P NMR spectra. The reaction of IIa with nickel acetate gives a diamagnetic bischelate complex of the type [Ni(ON) 2 ] , in which the deprotonated 1-amino-3-one-1-butenyl moiety acts as a bidentate O,N ligand.
N-protonated 2-pyridylnickel(II) complexes insertion of isocyanides into the nickel2-pyridyl bond
The reaction of the binuclear complex [NiCl(μ-2-py)(PPh3)]2 (μ-2-py = μ-C5H4N-C2,N) with the phosphines L (L = PPh3, PMePh2, PMe2Ph or PEt3) or dppe (= 1,2-bis(diphenylphosphino)ethane) in the presence of HClO4 yields the N-protonated 2-pyridyl derivatives trans-[NiCl(2-pyH)(L)2]ClO4 or [NiCl(2-pyH)(dppe)] ClO4 (2-pyH = C5H5N-C2) with a square-planar coordination around the nickel(II) center. These products are largely associated through hydrogen bonding between the NH group and the perchlorate anion, both in the solid and in chlorinated solvents. The configuration in solution has been studied by 1H and 31P NMR spectroscopy. In the complex trans-[NiCl(2-pyH)(PMe2Ph)2]ClO4, the planar 2-pyH…
Insertion of isocyanides into the palladium-(2-pyridyl) bond
The reaction of the pyridyl-bridged binuclear complex [PdBr(μ-2-C5H4N)(PPh3)]2 with isocyynides CNR (R p-C6H4OMe, Me, C6H11) yields the complex PdBr{(&2.dbnd;NR)C(&2.dbnd;NR) (2-C5H4N)}(PPh3)] containing a C,N-chelated 1,2-bis(imino)-2-(2-pyridyl)ethyl group, which results from successive insertions of two isocyanides molecules into the palladium2-pyridyl bond. The mononuclear compound trans-[PdBr(2-C5H4N)(PMePh2)2] readily reacts with various CNR ligands (R p-C6H4OMe, Me, C6H11, CMe3) to give the imino(2-pyridyl)methylpalladium(II) derivatives, trans-[Pdbr{C(=NR)(2-C5H4N)} (PMePh2)2].
Role of Halide Ion in the Mechanism of Protonolysis of the Pt-C Bond in Pt(II) Alkyl and Aryl Complexes.
Abstract A mechanistic study is described for the electrophilic cleavage of the Pt C σ bond in complexes cis -[PtPh 2 (PEtPh 2 ) 2 ] and trans -[PtXR(PEt 3 ) 2 ] (X = Cl and Br, R = Me, Et, n-Pr, n-Bu, CH 2 Ph) by the proton in the presence of halide ions in aqueous methanol (MeOH/H 2 O, 91v/v) which yields cis -[PtClPh(PEtPh 2 ) 2 ] and trans -[PtX 2 (PEt 3 ) 2 ], respectively. The reactions are first-order in substrate for both systems and the general bivariate rate law k obs = [H + ]{ k H + k x K [[X − ]}/(1 + K [[X − ]) is obeyed. The proposed mechanism involves a fast pre-equilibrium formation (K) of a platinum(II) anionic intermediate via interaction of the halide with the square-plan…
INSERTION OF ISOCYANIDES INTO THE PALLADIUM CARBON BOND OF C-2-PALLADATED HETEROCYCLES - SYNTHESIS OF TRANS-[PDCL(C(RN)=NR) (PPH3)2] COMPLEXES (RN = 2-PYRIDYL, 2-PYRAZYL - R = ALKYL OR ARYL GROUP)
The titles complexes trans-[PdCl{C(RN)NR}(PPh3)2] (RN = 2-pyridyl (2-py), R = p-C6H4OMe, Me; RN = 2-pyrazyl (2-pyz), R = p-C6H4OMe) can be prepared by reaction of the N-protonated compounds, cis-[PdCl2(RNH)(PPh3] (RNH = 2-pyridylium (2-pyH) or 2-pyrazylium (2-pyzH) group), with PPh3, followed by addition of the isocyanide CNR and deprotonation with triethylamine, in a molar ratio Pd/PPh3/CNR/NEt3 of 1/1/1/1.1. The reaction sequence involves the successive formation of the cationic intermediates trans-[PdCl(RNH)(PPh3)2]+, trans-[Pd(RNH)(CNR)(PPh3)2]2+ and trans-[Pd(RN)(CNR)(PPh3)2]+, which were isolated and characterized as perchlorate salts for RN = 2-pyridyl. In the final step the coordin…