Bis Axial Ligation of Simple Imine and Methyleneamido Groups by Ruthenium Porphyrins

Ruthenium Porphyrins with Axial π‐Conjugated Arylamide and Arylimide Ligands

“…The reactions of [Ru VI (por)O 2 ] with alkylamines6d, 22, 23 and amino esters24 were reported to afford bis(amine)ruthenium(II) porphyrins. Other related reactivity of [Ru VI (por)O 2 ] include the reaction with benzophenone imine to give [Ru IV (por)(N=CPh 2 ) 2 ]22b or [Ru II (por)(NH=CPh 2 ) 2 ],25 and the reaction with 1,1‐diphenylhydrazine to give [Ru IV (por)(NHNPh 2 ) 2 ] 26…”

Nitrido Ruthenium Porphyrins: Synthesis, Characterization, and Amination Reactions with Hydrocarbon or Silyl Enol Ethers

“…Ruthenium porphyrins constitute an unmatched family of metalloporphyrin that exhibits extraordinary versatility in binding N‐donating ligands at the axial sites 1–5. A wide variety of ruthenium porphyrins featuring axial RuN bonds have been prepared, including those bearing amine,1c, 3a,3b amido,3b–d,g imido,3a,c–e,g,j imine,3h, 4 methyleneamido,3h nitrile,1a, 2 hydrazido,3f nitrosoarene,1b, 3i nitrosyl,5 and dinitrogen1d axial ligands (Scheme , a – j ). This makes the lack of isolable ruthenium porphyrins with terminal nitrido axial ligands (Scheme 1, k ) especially conspicuous 6.…”

“…The reaction between [Ru VI (3,4,5‐MeO‐tpp)(O) 2 ] and HNC t Bu 2 to form 1 b contrasts sharply with that between the same dioxo complex and HNCPh 2 , the latter reaction has been reported to produce bis(methyleneamido) ruthenium( IV ) porphyrin [Ru IV (3,4,5‐MeO‐tpp)(NCPh 2 ) 2 ] in ≈65 % yield under similar conditions 3h…”

Synthesis of Aza‐Heterocycles from Oximes by Amino‐Heck Reaction

“…Alkylideneaminometal species have rarely been utilized in organic synthesis because of the difficulty in generating such species;5,6 however, they are attractive intermediates for the synthesis of amino compounds. Buchwald and colleagues7a and Hartwig and colleagues7b recently reported the palladiumcatalyzed amination of aryl halides via alkylideneamino(aryl)palladium(II) species that were generated from arylpalladium(II) halides and diphenylmethylideneamine by ligand exchange (Eq.…”

“…In the Heck reaction, sp 2 ‐carbopalladium species a play an important role as a key intermediate in the catalytic process, and oxidative addition can generate a variety of them from different types of alkenyl and aromatic compounds. To the best of our knowledge, however, there is no example of formation of sp 2 ‐aminopalladium (alkylideneaminopalladium) species by oxidative addition of corresponding sp 2 ‐amino‐X compounds 5,6. Such species have been prepared only by alkylideneamination of palladium (II) species with imines7 ( vide infra ).…”