Chiral phosphonite ligands (S,Rb)-5a, (S,Sb)-5b, (R,Rb)-6a and (R,Sb)-6b are introduced, comprising a MOP-type backbone with a binol-based binaphthyl group bound to the phosphorus. Their reaction with [Pd(η3-C4H7)Cl]2 affords η3-methallylpalladium chloride complexes 7a/b and 8a/b which have been isolated and structurally characterised. Solid-state and solution studies indicate subtle differences in their coordination behaviour, which ultimately affects their efficacy in the asymmetric hydrosilylation of styrene.