The Reaction of Re3Br9 with P(CH2OH)(3): Diversity of Modes of Coordination of Hydroxymethylphosphine to Clusters

The reaction of Re3Br9 with P(CH2OH)(3) (THP) in methanol under inert atmosphere gives a new cluster complex, [Re-3(mu(2)-Br)(3)Br-3(mu(3)-P,O,O-P(CH2OH)(CH2O)(2))(2)H] center dot 0.8H(2)O center dot 1.6MeOH (I). With access of air, the reaction produces a different product, [{Re-3(mu(2)-Br)(3)Br-2(OCH2)(2)PCH2-OP(CH2OH)(2)}(2)-{(P(CH2OH)(CH2O)(2))}(2)] (II), in which two triangular clusters are linked by deprotonated THP molecules as bridging ligands. In addition, each cluster is coordinated in a tetradentate fashion by the phosphine-phosphinite ligand, resulting from the oxidative condensation of two THP molecules (CIF files CCDC 1829565 (I) and 1829566 (II)).