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Bis(diphenylphosphino)methane

1,1-Bis(diphenylphosphino)methane (dppm), is an organophosphorus compound with the formula CH<sub>2</sub>(PPh<sub>2</sub>)<sub>2</sub>. Dppm, a white, crystalline powder, is used in inorganic and organometallic chemistry as a ligand. It is more specifically a chelating ligand because it is a ligand that can bond to metals with two phosphorus donor atoms. The natural bite angle is 73°.

Synthesis and reactivity

1,1-Bis(diphenylphosphino)methane was first prepared by the reaction of sodium diphenylphosphide (Ph<sub>2</sub>PNa) with dichloromethane:

Ph<sub>3</sub>P + 2 Na → Ph<sub>2</sub>PNa + NaPh
2NaPPh<sub>2</sub> + CH<sub>2</sub>Cl<sub>2</sub> → Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2</sub> + 2 NaCl

The methylene group (CH<sub>2</sub>) in dppm (and especially its complexes) is mildly acidic. The ligand can be oxidized to give the corresponding oxides and sulfides CH<sub>2</sub>[P(E)Ph<sub>2</sub>]<sub>2</sub> (E = O, S). The methylene group is even more acidic in these derivatives.

Coordination chemistry

As a chelating ligand, 1,1-bis(diphenylphosphino)methane forms a four-membered ring with the constituents MP<sub>2</sub>C. The ligand promotes the formation of bimetallic complexes that feature five-membered M<sub>2</sub>P<sub>2</sub>C rings. In this way, dppm promotes the formation of bimetallic complexes. One such example is the dipalladium chloride, Pd<sub>2</sub>Cl<sub>2</sub>(dppm)<sub>2</sub>. In this complex, the oxidation state for the Pd centres are I. Bis(diphenylphosphino)methane gives rise to a family of coordination compounds known as A-frame complexes.

References