Synthesis, structure, and reactivity of platinum compounds featuring terminal amido and phosphido ligands

Catalytic Synthesis of an Unsymmetrical PNP-Pincer-Type Phosphaalkene Ligand

“…Because the P2–C2 bond is saturated (1.879(2) Å), the P2 unit can be identified as a phosphanido ligand, formed by protonation at the C2 atom of the parent phosphaethenyl group. The sum of the bond angles around P2 is 298.81°; this value is among the smallest of terminal phosphanido complexes of platinum (306–333°) . Moreover, since the C2–P2–Pt bond bends to nearly 90° (89.30(13)°), the least contribution of the s-orbital of phosphorus to the Pt–P2 bond is suggested.…”

Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P4fragmentation

“…Even when acting as simple 'spectator' ligands, their properties as very strong σ and π donors can dramatically influence the electronic structure and hence the reactivity at the metal. 1 In addition, the presence of sterically and electronically accessible lone pairs of electrons leads to highly reactive metal-phosphorus bonds, [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] allowing for additional, 'non-innocent' reactivity toward substrates including Brønsted acids, 4,[10][11][12]17 electrophiles, 4,7,10,17 and unsaturated π systems. 19 Moreover, terminal phosphanido complexes can serve as metalloligands for heterobimetallic complexes.…”

Mechanism of intramolecular transformations of nickel phosphanido hydride complexes

“…[4][5][6][7][8] For example, there have been several reports of catalytic hydrophosphination by reactions of activated olefins with secondary phosphines catalyzed by Pt/Pd complexes. [1][2][3][9][10][11][12][13][14][15][16][17] However, similar reactions catalyzed by Ni-based complexes are more promising due to their lower cost. There has therefore been continuous interest in developing such systems.…”