Met­al cat­a­lysts are pop­u­lar for use in var­i­ous chem­i­cal reac­tions, par­tic­u­lar­ly those car­ried out on a large scale in indus­try. Com­mon tran­si­tion met­al cat­a­lysts such as Ruthe­ni­um and Pal­la­di­um often uti­lize phos­phine lig­ands for sta­bil­i­ty dur­ing the reac­tion. This occurs after a com­plex of a tran­si­tion met­al cat­a­lyst is formed with a phos­phine lig­and. Before we learn more about these com­plex­es, let’s explore the basics of phos­phine lig­ands.

What is phosphine ?

phosphineThis one name refers to three dif­fer­ent com­pounds (or groups of chem­i­cals). First, it refers to phos­phine gas which is out of the scope of this arti­cle. Sec­ond, it refers to a group of organophos­phine com­pounds with the chem­i­cal for­mu­la PRnH3-n. Accord­ing to the val­ue of n’, these are clas­si­fied as pri­ma­ry (n=1), sec­ondary (n=2) and ter­tiary (n=3) phos­phines. Metal phosphineThis is where the third clas­si­fi­ca­tion comes in. A class of ter­tiary phos­phines (PH3) is typ­i­cal­ly also referred to as phos­phines or phos­phine lig­ands’. These are aryl and alky derivates of phos­phines, used as lig­ands for tran­si­tion met­al cat­a­lysts. Phos­phine lig­ands are cat­e­go­rized as L-type’ lig­ands as these are derived from pre­cur­sors which were charge-neu­­tral. As lig­ands, these com­pounds can sta­bi­lize a range of met­als by form­ing met­al phos­phine com­plex­es.

Met­al phos­phine complexes

Sev­er­al met­al com­plex­es use organophos­phine com­pounds as lig­ands. These com­plex­es are lipophilic with good sol­u­bil­i­ty in organ­ic sol­vents. Fur­ther­more, they are also com­pat­i­ble with met­als in dif­fer­ent oxi­da­tion states. These two prop­er­ties make them par­tic­u­lar­ly use­ful in homo­ge­neous catal­y­sis, and in some cas­es, het­ero­ge­neous catal­y­sis too. These com­plex­es are both σ-donors and π-accep­­tors.

How are these prepared ?

The charge of a met­al com­plex remains unchanged after addi­tion of a lig­and. Phos­phine lig­ands can be added to an unsat­u­rat­ed met­al pre­cur­sor or through dis­place­ment of anoth­er bound lig­and. For instance, pal­la­di­um chlo­ride is treat­ed with triph­enylphos­phine to form bis(triphenylphosphine)palladium(II) chlo­ride.

Bond­ing and reaction

Phos­phine lig­ands inter­act as Lewis bases with met­al cat­a­lysts, func­tion­ing as σ donor lig­ands. After com­plex for­ma­tion, they work as spec­ta­tors rather than actors in the reac­tion. Gen­er­al­ly, the only action one sees is the dis­so­ci­a­tion of the lig­and from the com­plex. Oth­er class­es of phos­phines, pri­ma­ry and sec­ondary, are also used as lig­ands in some cas­es.

Com­mon­ly used phos­phine ligands

A num­ber of phos­phine lig­ands are pop­u­lar for use in var­i­ous reac­tions. For exam­ple, Xant­phos is a biden­tate lig­and which forms com­plex­es with plat­inum chlo­ride. Such lig­ands are com­mon­ly used for hydro­formy­la­tion of alkenes. Here are the most com­mon­ly used lig­ands avail­able at Wat­son International :  If you’re look­ing for high puri­ty phos­phine lig­ands and homo­ge­neous or het­ero­ge­neous cat­a­lysts, then you are at the right place. Call us or order online.