Bite angle

The structure of the backbone and the substituents attached to the phosphorus atoms influence the chemical reactivity of the diphosphine ligand in metal complexes through steric and electronic effects.

[7] Larger cone angles usually result in faster dissociation of phosphine ligands because of steric crowding.

The bite angle of a diphosphine ligand also indicates the distortion from the ideal geometry of a complex based on VSEPR models.

[9][10] One intermediate, [Rh(H)(alkene)(CO)L], exists in two different isomers, depending on the position of phosphine ligands (Figure 4).

[9] Diphosphine ligands such as dppe, which has a bite angle of about 90°, span the equatorial and apical positions (AE isomer).

Diphosphines with larger bite angles (above 120°) preferentially occupy a pair of equatorial positions (EE isomer).

With a bite angle of approximately 113°, BISBI spans sites on equatorial plane of the trigonal bipyramidal intermediate complex (Figure 6).

The bite angle affect the steric crowding at the Rh atom that results from the interactions of the bulky backbone of the ligand with substrate.

The wide bite angle that results from the backbone allows the five-coordinate [Rh(H)(diphosphine)CO(alkene)] intermediate to adopt a structure that relieves steric hindrance.

This increased electron density would be available for π-donation into the anti-bonding orbitals of other ligands, which could weaken other M-L bonds within the catalyst, leading to higher rates.

The two phosphorus atoms (orange) of dppe have a bite angle of 85.8° on the palladium atom (blue) in [PdCl 2 (dppe)].
Figure 1. Dicylohexylphosphinomethane, dcpm, which forms a four-membered chelate ring.
Figure 2. DPEphos, which forms an eight-membered chelate ring.
Figure 3. Bite angle of a diphosphine ligand bound to rhodium .
Figure 4. EA and EE isomers of Rh(H)(alkene)(CO)L.
Figure 5. BISBI, a diphosphine with a bite angle of 113°.
Figure 6. BISBI occupies sites on the equatorial plane.