Chiral phosphonite ligands (S,R b )-5a, (S,S b )-5b, (R,R b )-6a and (R,S b )-6b are introduced, comprising a MOP-type backbone with a binol-based binaphthyl group bound to the phosphorus. Their reaction with [Pd(η 3 -C 4 H 7 )Cl] 2 affords η 3 -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

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... metric hydrosilylation of styrene. † Electronic supplementary information (ESI) available: Full experimental and crystallographic data. CCDC reference numbers 840097 (7a), 840098 (7b), 854373 (8a) and 840100 (8b). For ESI and crystallographic data in CIF or other electronic format see