In one aspect, phosphine compounds comprising three adamantyl moieties (PAd3) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAd3 ligands are also provided for catalytic synthesis including catalytic cross-coupling reactions.