Palladacycles derivates of diimines ligands [N,C,C,N]

In past years extensive work has been published on double cyclometallated complexes containing two independent metallated phenyl rings.[1-4] In spite of such a wide range of publications, relatively few studies deal with double metallation of the same phenyl ring. In order to make this possible, it is necessary for the ligand to contain two substituents with potentially donor atoms, such as nitrogen or sulfur, which allow the formation of two five− or six− membered chelate rings. This paper describes the preparation, characterization and structural study of novel tridentate [C,N,S] biscyclopalladated complexes with ligands derived from the condensation of a primary amine −2-(methylthio)aniline− with the corresponding aromatic dialdehyde −terephthalaldehyde−. The compounds are also interesting due to their close-to-planarity arrangement and to the presence of seven fused rings in their structure.

[1]  B. Coe,et al.  Tetrapalladium(II) Bisazobenzene and Azoazoxybenzene Complexes: Syntheses, Electronic Structures, and Optical Properties , 2011 .

[2]  Jesús J Fernández,et al.  Dimetalated Crown Ether Schiff Base Palladacycles. Influence of the Carbon Chain Length on the Coordination Mode of Bidentate Phosphines. Crystal and Molecular Structure of the Novel Complex [Pd2{1,4-[C(H)═N{9,10-(C8H16O5)C6H3}]2C6H2-C2,C5}(Cl)2{μ-Ph2P(CH2)5PPh2}2] , 2011 .

[3]  Jesús J Fernández,et al.  The chemistry of N-benzylidene-1,4-phenylenediamine palladacycles: The crystal and molecular structure of the first tetranuclear palladacycle with bridging Ph2PCH2PPh2 ligands , 2009 .

[4]  R. Navarro,et al.  Synthesis and structure of tetranuclear orthometallated Pd(II) complexes derived from bis-iminophosphoranes. , 2008, Dalton transactions.

[5]  J. Rourke,et al.  Cyclometallated nitrogen heterocycles , 2003 .

[6]  M. Graña,et al.  CBr versus CH bond activation in palladium(II) cyclopalladated compounds. , 2002 .

[7]  Jesús J Fernández,et al.  Mixed Triply and Doubly Bridged Dinuclear Palladium(II) Cyclometalated Compounds. Crystal and Molecular Structures of [1,3-{Pd[2,3,4-(MeO)3C6HC(H)NCH2](μ-O2CMe)}2C6H4] and [1,4-{Pd[2,3,4- (MeO)3C6HC(H)NCH2](Cl)}2C6H4(μ-Ph2P(CH2)3PPh2)] , 2002 .

[8]  J. Rourke,et al.  Doubly cyclopalladated pyridazines: chiral liquid crystals , 2002 .

[9]  Jesús J Fernández,et al.  Cyclometalated Palladium(II) Fragments as Building Blocks in the Construction of New Heteronuclear Metalomacrocycles , 2001 .

[10]  H. Adams,et al.  Polynuclear cyclometallated palladium (II) complexes derived from potentially hexadentate Schiff base ligands. Crystal structures of [(Cl)Pd{Me2NCH2CH2N(H)C}C6H2{C(H)NCH2CH2NMe2}Pd(Cl)] and [{(Ph2PCH2CH2)2PPh-P,P,P}Pd{Me2NCH2CH2N(H)C}C6H2{C(H)NCH2CH2NMe2}Pd{(Ph2PCH2CH2)2PPh-P,P,P}][Cl]2 , 2000 .

[11]  P. Steel,et al.  Cyclometallated compounds. XIII. Cyclopalladation of 2-phenoxypyridine and structurally-related compounds , 1999 .

[12]  G. Bernardinelli,et al.  Cyclometallated fragments as building blocks for self-assembly reactions , 1997 .

[13]  M. Alonso,et al.  Cyclometallated compounds of Pd(II) with pyrazole derivatives. Unusual double palladation of diarylbis(N-pyrazolyl)methanes , 1994 .

[14]  P. Steel,et al.  Cyclometallated compounds: VIII. Double cyclopalladation of diacetylbenzene dioximes and 1,5-bis(dimethylamino)naphthalene , 1991 .

[15]  P. Steel,et al.  Cyclometallated compounds. V, Double cyclopalladation of diphenyl pyrazines and related ligands , 1990 .

[16]  Montserrat Gómez,et al.  Chiral bis(oxazoline) ligands. Synthesis of mono- and bi-metallic complexes of nickel and palladium , 1998 .

[17]  K. K. Nanda,et al.  Doubly cyclopalladated complexes of N,N,N′,N′-tetraethylbenzene-1,3-bis(methylamine) , 1992 .