Transition-metal–carbon bonds. Part 45. Attempts to cyclopalladate some aliphatic oximes, NN-dimethylhydrazones, ketazines, and oxime O-allyl ethers. Crystal structures of [Pd₂{CH₂C(CH₃)₂C(NOH)CH₃}₂Cl₂] and [Pd{CH₂C(NNMe₂)C(CH₃)₃}(acac)]

Abstract

Transition-metal-Carbon Bonds. Part 45.' Attempts t o Cyclopalladate Some Aliphatic Oximes, NN-Dimethylhydrazones, Ketazines, and Oxime 0-Ally1 Ethers. Crystal Structures of [ P ~~( C H ~C ( C H ~) ~C ( = N O H ) C H ~) Z C I ~] and [Pd(CH2C(=NNMe2)C(CH3)3)(acac)] t

The Scope of Ambiphilic Acetate‐Assisted Cyclometallation with Half‐Sandwich Complexes of Iridium, Rhodium and Ruthenium

“…To our knowledge this is the first structure of a cyclometallated aldehyde oxime, though there are two structures of cyclopalladated ketoximes. [20] The M À N and M À C bond lengths, which are approximately the same [2.048(5) and 2.045(6) , respectively], are slightly shorter than the corresponding distances in 1 a and 3 a described above. There is intermolecular hydrogen bonding between the OH group of one molecule and a Cl group of another to form hydrogen-bonded dimers (O À H … Cl 2.250 ).…”

Metal-catalysed halogen exchange reactions of aryl halides

“…It has been known for a long time that treatment of organopalladium(II) complexes with oxidising agents induces reductive elimination of functionalised organic molecules from the metal centre, and this has been used for the stoichiometric palladium-mediated functionalisation of 5 unactivated C-H bonds in many cases. [56][57][58][59] There is very good evidence that the reactions in Scheme 17 proceed via a Palladium(II)/Palladium(IV) catalytic cycle. Thus, coordination of the directing group to the Pd(II) species facilitates C-H activation on the aromatic ring to give an 10 arylpalladium species (Scheme 18, 84).…”

Structure of di-μ-chlorobis(dicarbonylpalladium)

“…The mean Pd--C bond length of 1.852 (10)A is significantly shorter than the values 2.023 (6) and 2.052 (8)A found in di-#-chloro-bis[(3-hydroxyimino-2,2-dimethylbutyl-CI,N)-palladium(II)] (Constable, McDonald, Sawkins & Shaw, 1980) and bis~-* Lists of structure amplitudes, anisotropic thermal parameters and least-squares-planes calculations have been deposited withthe British Library Document Supply Centre as Supplementary Publication No, SUP 44020 (7 pp.). Copies may be obtained through The Executive Secretary, International Union of Crystallography, 5 Abbey Square, Chester CH 1 2HU, England.…”