0000000000309360
AUTHOR
B. Crociani
Organometallic nucleophiles. Mechanism of halide displacement at saturated carbon by 2-pyridyl and 4-Pyridyl complexes [M(dmtc)(C5H4N-Cn)(L)] (M Pd, Pt; dmtc dimethyldithiocarbamate; n 2,4; L
Abstract A mechanistic study is reported of nucleophilic halide substitution by pyridyl complexes [M(dmtc)C 5 H 4 N- C 2 )(L)] (M Pd or Pt; L PMe 3 , PEt 3 or PPh 3 ) and [Pd(dmtc)C 5 H 4 N- C 4 )(L)] (L PMe 3 or PPh 3 ) on organic halides XCH 2 R (X Cl or Br; R CHCH 2 , COMe, Ph, or CN) in various solvents, yielding the pyridylium derivatives [M(dmtc)1-CH 2 R)C 5 H 4 N- C 2 (L)] + and [Pd(dmtc)(1-CH 2 R)(C 5 H 4 N- C 4 (L)] + , respectively. The kinetics obey a second-order rate law: rate k 2 [XCH 2 R][Complex]. A similar rate law is observed for the analogous reactions involving 4-dimethyl-aminopyridine (4-dmapy) as the nucleophile. The effects of solvent and leaving group, a…
Organometallic nucleophiles.A mechanistic study of halide displacement at saturated carbon by 2- and 4-pyridyl complexes of palladium (II) and platinum (II)
Abstract The reactions of the 2- and 4-pyridyl complexes [MX(C 5 H 4 N C n )(dppe)] and trans -[MX(C 5 H 4 N C n )(PPh 3 ) 2 ] (M Pd, Pt; X Cl, Br; n = 2, 4)- involving halide displacement from the organic halides XCH 2 R (X Cl, Br; R CN, Ph, CH CH 2 ) by the pyridyl nitrogen have been studied kinetically by conductivity in acetone or acetonitrile at 25°C. The kinetic data fit the second-order rate law rate k 2 [XCH 2 R][complex], in agreement with an S N 2 process at saturated carbon. The higher rates are displayed by the 2-pyridylplatinum derivatives with X Br in both the metal complex and the organic halide. The higher nucleophilic power of the 2-pyridyl complexes compare…
Mechanism of oxidative allyl transfer from allylic ammonium cations to palladium(0) α-diimine complexes
Abstract The palladium(0) complex [Pd(η2-fn)(NN′)] (1, fn = fumaronitrile; NN′ = C5H4N-2-CH=NC6H4OME-4) reacts slowly and reversibly with A + CH 2 CH=CH 2 (2a, A = NEt 3 ; 2 b , A = C 5 H 5 N ) to yield the cationic η3-allypalladium(II) derivative [ Pd (η[ 3 - C 3 H 5 )( N N ′)] + (3) the free amine A and fn. The equilibrium constant Ke is (2.6 ± 0.1) × 10−3 for 2a and 1.0 ± 0.4 for 2b. Kinetic studies of these oxidative allyl-transfer reactions show that the rates increase with increasing concentration of 2 and with decreasing concentration of fn. A stepwise mechanism is proposed which involves slow and reversible displacement of fn by 2 to give a labile intermediate [ Pd (η 2 - CH…
Five-coordinate complexes of palladium(ii) and platinum(ii) with α-diimine and 1,5-cyclooctadiene ligands
The five-coordinate complexes [PtMe(cod)(N–N′)]BF4 [cod = η2,η2-cyclooctadiene, N–N′ = (6-R2)C5H3N-2-CHNR1 (R1 = C6H4OMe-4, R2 = H (1), Me (2); R1 = CMe3, R2 = H (3), Me (4); R1 = (R)-bornyl, R2 = Me (5))] are readily obtained from the reaction of [PtClMe(cod)] with N–N′ in the presence of NaBF4. The preparation of [PtMe(cod)(6)]BF4 (6 = 4-MeOC6H4NCHCHNC6H4OMe-4), [PdMe(cod)(N–N′)]BF4 and [PtCl(cod)(N–N′)]BF4 (N–N′ = 2, 4) requires chloride abstraction by AgBF4 from [PtClMe(cod)], [PdClMe(cod)] and [PtCl2(cod)], respectively, followed by coordination of N–N′. The NMR spectral data suggest a trigonal-bipyramidal structure with chelating cod and N–N′ ligands, where the α-diimine and one CC bo…
Isomer Distribution and Interconversion in Cationic Allylpalladium(II) Complexes with 2-(Iminomethyl)pyridine Ligands
The complexes [Pd(η3-allyl)(N-N‘)]ClO4 [allyl = 2-butenyl or 3-methyl-2-butenyl, N-N‘ = C5H3(6-R)N-2-CHNR‘ (R = H, R‘ = Me, CMe3, C6H4OMe-4; R = Me, R‘ = C6H4OMe-4) and C5H4N-2-CH2NMe2] are present in solution with different isomers, the structures of which may be assigned by an 1H NMR criterion based on chemical shift changes of the pyridine H(6) and/or of the allylic methyl protons, as confirmed also by 2D 1H NMR spectra. The isomer distribution depends mainly on the steric requirements of both the allyl and N-N‘ ligands: for [Pd(η3-3-methyl-2-butenyl)(N-N‘)]ClO4 the predominant isomer (ca. 100%) has a structure with the allylic methyl groups cis to the coordinated pyridine nitrogen when…
CCDC 176254: Experimental Crystal Structure Determination
Related Article: F.Di Bianca, G.Bandoli, A.Dolmella, S.Antonaroli, B.Crociani|2002|J.Chem.Soc.,Dalton Trans.||212|doi:10.1039/b106247f