Hydroxylated phosphines as ligands for chalcogenide clusters: Self assembly, transformations and stabilization

© 2017 IUPAC & De Gruyter.This contribution is a documentation of recent advances in the chemistry of chalcogenide polynuclear transition metal complexes coordinated with mono-and di-phosphines functionalized with hydroxo groups. A survey of complexes containing tris(hydroxymethyl)phosphine (THP) is presented. The influence of the alkyl chain in bidentate phosphines, bearing the P-(CH2)x-OH arms, is also analyzed. Finally, isolation and structure elucidation of the complexes with HP(OH)2, P(OH)3, As(OH)3, PhP(OH)2, stabilized by coordination to Ni(0) and Pd(0) centers embedded into chalcogenide clusters, is discussed

The Reaction of Re<inf>3</inf>Br<inf>9</inf> with P(CH<inf>2</inf>OH)<inf>3</inf>: Diversity of Modes of Coordination of Hydroxymethylphosphine to Clusters

© 2019, Pleiades Publishing, Ltd. Abstract: The reaction of Re3Br9 with P(CH2OH)3 (THP) in methanol under inert atmosphere gives a new cluster complex, [Re3(µ2‑Br)3Br3(µ3-P,O,O-P(CH2OH)(CH2O)2)2H] ∙ 0.8H2O · 1.6MeOH (I). With access of air, the reaction produces a different product, [{Re3(µ2-Br)3Br2(OCH2)2PCH2-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))

The Reaction of Re<inf>3</inf>Br<inf>9</inf> with P(CH<inf>2</inf>OH)<inf>3</inf>: Diversity of Modes of Coordination of Hydroxymethylphosphine to Clusters

© 2019, Pleiades Publishing, Ltd. Abstract: The reaction of Re3Br9 with P(CH2OH)3 (THP) in methanol under inert atmosphere gives a new cluster complex, [Re3(µ2‑Br)3Br3(µ3-P,O,O-P(CH2OH)(CH2O)2)2H] ∙ 0.8H2O · 1.6MeOH (I). With access of air, the reaction produces a different product, [{Re3(µ2-Br)3Br2(OCH2)2PCH2-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))

Hydroxylated phosphines as ligands for chalcogenide clusters: Self assembly, transformations and stabilization

© 2017 IUPAC & De Gruyter.This contribution is a documentation of recent advances in the chemistry of chalcogenide polynuclear transition metal complexes coordinated with mono-and di-phosphines functionalized with hydroxo groups. A survey of complexes containing tris(hydroxymethyl)phosphine (THP) is presented. The influence of the alkyl chain in bidentate phosphines, bearing the P-(CH2)x-OH arms, is also analyzed. Finally, isolation and structure elucidation of the complexes with HP(OH)2, P(OH)3, As(OH)3, PhP(OH)2, stabilized by coordination to Ni(0) and Pd(0) centers embedded into chalcogenide clusters, is discussed

Cd²⁺ Complexation with P(CH₂OH)₃, OP(CH₂OH)₃, and (HOCH₂)₂PO₂^–: Coordination in Solution and Coordination Polymers

The coordination of Cd²⁺ with P­(CH₂OH)₃ (THP) in methanol was followed by ³¹P and ¹¹¹Cd NMR techniques. A cadmium-to-phosphine coordination ratio of 1:3 has been established, and effective kinetic parameters have been calculated. Air oxidation of THP in the presence of CdCl₂ at room temperature produces coordination polymer ³_∞[Cd₃Cl₆(OP­(CH₂OH)₃)₂] (<b>1</b>). The same oxidation reaction at 70 °C gives another coordination polymer, _∞[CdCl₂(OP­(CH₂OH)₃)] (<b>2</b>). Complexes <b>1</b> and <b>2</b> are the first structurally characterized complexes featuring OP­(CH₂OH)₃ as a ligand that acts as a linker between Cd atoms. The addition of NaBPh₄ to the reaction mixture gives coordination polymer _∞[Na₂CdCl₂(O₂P­(CH₂OH)₂)₂(H₂O)₃] (<b>3</b>) with (HOCH₂)₂PO₂^– as the ligand. Coordination polymers <b>1</b>–<b>3</b> have been characterized by X-ray analysis, elemental analysis, and IR spectroscopy