Ortho-metallated transition metal complexes derived from tertiary phosphine and arsine ligands

ortho‐Metalation of Iron(0) Tribenzylphosphine Complexes: Homogeneous Catalysts for the Generation of Hydrogen from Formic Acid

“…To the best of our knowledge orthometalation of iron(0)/phosphine complexes is only known with 1,2-bis(diphenylphosphine)ethane (dppe) as the ligand. [10] Four-membered metallacycles can be formed thermally and photochemically when either [Fe(dppe) 2 (C 2 H 4 )] or [Fe(dppe) 2 H 2 ] are used as precursors. [11] Such structures can be effectively used for the activation of C(sp)ÀH bonds.…”

Synthesis and characterization of 2-phenylaniline cyclopalladated complexes

“…The cyclopalladation reaction has been profusely investigated in view of the rich chemistry it renders and is well documented for a great variety of metal centers and ligands [1][2][3]. Cyclopalladated complexes have generated considerable interest due to their applications in organic and organometallic synthesis [4][5][6], photochemistry [7,8], optical resolution process [9,10], as biologically active compounds [11], liquid crystals [12,13] and mainly in homogeneous catalysis for the design of new materials with outstanding properties [4][5][6][14][15][16][17][18].…”

Rhodium‐Catalyzed PIII‐Directed ortho‐C−H Borylation of Arylphosphines

“…[4] Since then, many groups have reported on the synthesis,r eactivity,a nd structure of different transition-metal complexes containing ortho-metalated arylphosphines (ArPR 2 ). [5] Owing to the strong coordination between transition metals and tertiary phosphine groups,t he catalytic variant remained ac ritical challenge.R ecently,w ea nd other groups have successfully explored the use of the P III atom as ad irector in transition-metal-catalyzed C À Hactivation reactions,including the C À H functionalization of phenols (ArOP t Bu 2 ), [6] ferrocenebased, [7] biaryl, [8] and 1-naphthyl [9] phosphines,a sw ell as indoles (N-P t Bu 2 ). [10] Despite these successes,exquisite selectivity was only achieved through the generation of P IIIchelation-assisted five/six-membered-ring intermediates.A s anatural extension of this chemistry,webecame interested in the development of acatalytic process that could achieve the ortho-CÀHf unctionalization of PPh 3 and other arylphosphines based on the precedent stoichiometric reactions.…”