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RESEARCH PRODUCT
Preparation and reactivity of 1,2-bis(imino)ethylpalladium(II) complexes
Antonio MantovaniAlberto ScrivantiBruno Crocianisubject
MethylamineStereochemistryOrganic ChemistryCenter (category theory)chemistry.chemical_elementBiochemistryAdductInorganic ChemistryMetalchemistry.chemical_compoundchemistryvisual_artMaterials Chemistryvisual_art.visual_art_mediumReactivity (chemistry)ChelationEthyl groupPhysical and Theoretical ChemistryPalladiumdescription
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 of ancillary ligands at the palladium center of DABI by dimethyldithiocarbamate anion (dmtc) affords the complex [ P d ( dmtc ) { C ( = N R ) ︹ C H = N R } ( P P h 3 ) ] , DABIII. The DABI, DABII and DABIII derivatives react with anhydrous metal chlorides, MCl2 (M = Co, Ni, Cu, Zn) to give1/1 adducts in which the 1,2-bis(imino)ethyl group acts as a chelating bidentate ligand. Magnetic moment measurements and the far-infrared and electronic spectra of these binuclear compounds indicate an essentially pseudo-tetrahedral configuration at M. The reaction of DABI with [PdCl(η3-2-MeC3H4)]2, or [PtCl(C3H5)]4, (DABI/Pd or Pt ratio,1/2) involves the exchange of Cl− and PPh2 ligands, which leads to the formation of the zwitterionic binuclear derivatives [Pd(η3-2-MeC3H4)(DABIV)], or [ P t ( η 3 − C 3 H s ) ( D A B I V ) ] ( D A B I V = c i s − P d C I 2 { C ( = N R ) ︹ C H = N R } ( P P h 3 ) ) , and [PdCl(η3-2-MeC3H4)(PPh3)], or [PtCl(η3-C3H5)(PPh3)].
year | journal | country | edition | language |
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1982-07-01 | Journal of Organometallic Chemistry |