chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a physical science within the natural sciences that studies the chemical elements that make up matter and chemical compound, compounds made of atoms, molecules a ...

, phosphorochloridites are a class of

organophosphorus compound Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbo ...

with the formula (RO)₂PCl (R = organic substituent). They are pyramidal in shape, akin to regular

phosphite The general structure of a phosphite ester showing the lone pairs on the P In organic chemistry, a phosphite ester or organophosphite usually refers to an organophosphorous compound with the formula P(OR)3. They can be considered as esters of ...

s (P(OR)₃). They are usually colorless and sensitive toward hydrolysis and, to some extent, oxidation to the corresponding

phosphorochloridate In chemistry, a phosphorochloridate is a class of organophosphorus compounds with the formula (RO)2P(O)Cl (R = organic substituent). They are tetrahedral in shape, akin to regular phosphates (OP(OR)3). They are usually colorless and sensitive tow ...

s ((RO)₂P(O)Cl).

Synthesis and reactions

Phosphorochloridites are produced by partial

alcoholysis In chemistry, solvolysis is a type of nucleophilic substitution (S1/S2) or elimination where the nucleophile is a solvent molecule. Characteristic of S1 reactions, solvolysis of a chiral reactant affords the racemate. Sometimes however, the ster ...

phosphorus trichloride Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic ...

, which proceeds stepwise: :PCl₃ + ROH → HCl + (RO)PCl₂ (phosphochloridite) :(RO)PCl₂ + ROH → HCl + (RO)₂PCl (phosphodichloridite) :(RO)₂PCl + ROH → HCl + (RO)₃P (phosphite) These reactions are readily controlled with aromatic

diol A diol is a chemical compound containing two hydroxyl groups ( groups). An aliphatic diol may also be called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified. They are used as protecting gro ...

s, such as binaphthol and 2,2'-biphenol. Phosphorochloridites are precursors to diphosphite

ligand In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's el ...

s. When combined with rhodium precursors such as Rh(acac)(CO)₂, these diphosphite ligands afford catalysts that are used industrially for the

hydroformylation In organic chemistry, hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the production of aldehydes () from alkenes (). This chemical reaction entails the net addition of a formyl group () and a hydrogen ...

of alkenes. it and related ligands have become popular in hydroformylation catalysis.

References

{{Organophosphorus Functional groups Chlorides Phosphorus(III) compounds