Rhodium and iridium complexes of a new ferrocene-derived chelating bis(NHC) ligand.

Rhodium and iridium complexes of a new ferrocene-derived bis(N-heterocyclic carbene) ligand, [M(cod){1,2-(MeNCHCHNCCH(2))(2)C(5)H(3)}Fe(C(5)H(5))]BF(4) (M = Rh, 8a; M = Ir, 8b; cod = 1,5-cyclooctadiene), were synthesized from the corresponding bis(imidazolium) salt 6. The molecular structure of 8a was determined by single-crystal X-ray diffraction. Complexes 8a and 8b smoothly react with CO with displacement of the chelating cod ligand to give the corresponding dicarbonyl derivatives 9a and 9b.

Synthesis and characterization of fluorophenylpalladium pincer complexes: electronic properties of some pincer ligands evaluated by multinuclear NMR spectroscopy and electrochemical studies.

Palladium fluorophenyl complexes with different pincer ligands Pd(Ar)[2,6-(tBu(2)PCH(2))(2)C(6)H(3)] (13), Pd(Ar)[2,6-(tBu(2)PO)(2)C(6)H(3)] (14), Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))] (15), and Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Ru(C(5)H(5))] (16) were synthesized by the reaction of LiAr (Ar = C(6)H(4)F-4) with the respective trifluoroacetate palladium pincer complexes 9-12. The molecular structures of 14 and 16 were determined by an X-ray crystallographic method. Complexes 13-16 and {Pd(Ar)[{2,5-(tBu(2)PCH(2))(2)C(5)H(2)}Fe(C(5)H(5))]}PF(6) (17) were studied by multinuclear NMR spectroscopy and cyclic voltammetry.

An aza cyclopropylcarbinyl-homoallyl radical rearrangement-radical cyclization cascade. Synthesis of dibenzoimidazoazepine and oxazepine derivatives.

The cycloaddition of the dibenzoxazepinium W-ylides, generated by heating of trans-1-aryl-7,11b-dihydro-1H-azirino[1,2-a]dibenzo[c,f]azepines, to the C═N double bond of 3-aryl-2H-azirines proceeds endo-stereoselectively giving regioisomeric cycloadducts in ca. 1:1 ratio, in good overall yields. In contrast to the dibenzoxazepinium ylides, the cycloaddition of the dibenzazepinium W-ylide proceeds regioselectively but without exo-endo-stereoselectivity.

An efficient approach to azirino and pyrrolo-fused dibenzazepines. Conformations of substituted dibenzo[c,f]pyrrolo[1,2-a]azepines.

An effective approach to azepino-fused heterocycles is described. trans-1-Aryl-7,11b-dihydro-1H-azirino[1,2-a]dibenzo[c,f]azepines were synthesised via a domino sequence: isomerization of gem-dichloroaziridine-intramolecular Friedel-Crafts acylation of the tethered benzene ring catalysed by SnCl(4) and subsequent hydride induced intramolecular cyclization. Cycloaddition of dibenzazepinium ylides, generated by heating these aziridines, to activated C[double bond]C, C[triple bond]C dipolarophiles and fullerene C(60), leads to derivatives of dibenzo[c,f]pyrrolo[1,2-a]azepine.

Synthesis, catalytic activity, and photophysical properties of 5,6-membered Pd and Pt SCS'-pincer complexes based on thiophosphorylated 3-amino(hydroxy)benzoic acid thioanilides.

Novel unsymmetrical SCS'-pincer ligands, 1-[PhNHC(S)]-3-[Ph(2)P(S)NH]-C(6)H(4) (3) and 1-[PhNHC(S)]-3-[Ph(2)P(S)O]C(6)H(4) (7), bearing a thiocarbamoyl moiety in combination with thiophosphorylamino- and thiophosphoryloxy-donating groups, respectively, were obtained via thiophosphorylation of 3-amino- and 3-hydroxy-benzoic acid (thio)anilides 1 and 6. Direct cyclometallation of the central benzene ring in the ligands 3 and 7 in reaction with (PhCN)(2)MCl(2) (M = Pd, Pt) as a metal precursor afforded κ(3)-SCS'-hybrid pincer complexes 8, 9 with 5- and 6-membered fused metallacycles in good to high yields (67-95%). The complexes 8 and 9 were characterized by multinuclear NMR ((31)P, (1)H, (13)C) and IR spectroscopy as well as single-crystal X-ray crystallography.