MetalMetal Bond‐Containing Complexes as Catalysts for CH Functionalization

Homo- and heteroleptic group 4 2-(diphenylphosphino)pyrrolide complexes: Synthesis, coordination chemistry and solution state dynamics

“…While discrete synthetic examples containing metal-metal interactions have existed for decades, recent applications of multimetallic complexes in organometallic catalysis [4][5][6][7][8][9][10][11] and small molecule activation [12][13][14][15] have renewed significant interest in the fundamental structure, bonding and reactivity of this class of molecules, as well as the design and implementation of new bridging bifunctional supporting ligands.…”

Metal–metal multiple bonded intermediates in catalysis

“…The most spectacular of these catalytic reactions involve the insertion of a carbene or nitrene into unactivated C-H bonds (scheme 1). [3][4][5][6][7][8][9] These catalytic reactions are presumed to occur via the intermediacy of discrete Rh 2 -carbene or Rh 2 -nitrene complexes that feature a proposed linear Rh-Rh=E unit, where E = the carbene or nitrene fragment. Studies aimed at elucidating the mechanism of these reactions with special emphasis on the detection and spectroscopic characterization of the proposed Rh-Rh=E species, are reviewed here.…”

Iodide-enhanced palladium catalysis via formation of iodide-bridged binuclear palladium complex

“…he prevalence of the metalloenzymes containing binuclear or polynuclear transition metal complexes in their active sites has motivated the interest of chemists in the binuclear or polynuclear homogeneous catalysts for organic transformations [1][2][3][4][5][6][7][8][9][10] . A number of well-defined binuclear catalysts have been reported with unique activity and selectivity accessible through the cooperation between two metal centres 1,[4][5][6][8][9][10][11][12] .…”

“…he prevalence of the metalloenzymes containing binuclear or polynuclear transition metal complexes in their active sites has motivated the interest of chemists in the binuclear or polynuclear homogeneous catalysts for organic transformations [1][2][3][4][5][6][7][8][9][10] . A number of well-defined binuclear catalysts have been reported with unique activity and selectivity accessible through the cooperation between two metal centres 1,[4][5][6][8][9][10][11][12] . Two types of bimetallic cooperation are commonly encountered in the catalytic processes of these binuclear catalysts: one is the simultaneous activation of two reaction partners by the binuclear catalysts in which multidentate ligands hold two metal centres in close proximity to create two electronically discrete, conformationally advantageous active sites for binding the corresponding substrate molecules 1,4,5,13,14 , as illustrated by olefin polymerization 13 or enantioselective binuclear catalysts 5,14 ; the other is that two metal centres of the metal-metal bond-containing binuclear catalyst synergistically participate in elemental redox steps in catalytic pathways 6,9,10,[15][16][17][18][19][20][21][22][23][24]…”

“…A number of well-defined binuclear catalysts have been reported with unique activity and selectivity accessible through the cooperation between two metal centres 1,[4][5][6][8][9][10][11][12] . Two types of bimetallic cooperation are commonly encountered in the catalytic processes of these binuclear catalysts: one is the simultaneous activation of two reaction partners by the binuclear catalysts in which multidentate ligands hold two metal centres in close proximity to create two electronically discrete, conformationally advantageous active sites for binding the corresponding substrate molecules 1,4,5,13,14 , as illustrated by olefin polymerization 13 or enantioselective binuclear catalysts 5,14 ; the other is that two metal centres of the metal-metal bond-containing binuclear catalyst synergistically participate in elemental redox steps in catalytic pathways 6,9,10,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] , as exemplified by Pd(III) dimer-catalysed oxidative C-H functionalization [17][18][19] and dirhodium-catalysed reactions for carbene [20...…”