Transition-Metal Complexes Containing Parent Phosphine or Phosphinyl Ligands and Their Use as Precursors for Phosphide Nanoparticles

Susanne Bauer (1) , Cornelia Hunger (1) , Michael Bodensteiner (1) , Wilfried-Solo Ojo (2) , Arnaud Cros-Gagneux (2) , Bruno Chaudret (2) , Céline Nayral (2) , Fabien Delpech (2) , Manfred Scheer (3)

1 Institut für Anorganische Chemie
2 LPCNO - Laboratoire de physique et chimie des nano-objets
3 Institut für Anorganische Chemie

P–H functional transition-metal complexes were synthesized without using hazardous PH3 gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)6-x (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P2(SiMe3)4 and subsequent methanolysis to give the bridging complexes [(CO)xM(μ-PH2)]2 (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)4M(μ-PH2)]2 (M = Cr (2a), M = W (2b)) with P(SiMe3)3 was applied followed by methanolysis to synthesize the PH2 bridging transition-metal binuclear complexes with terminal PH3 groups. The products [(CO)4M(μ-PH2)2M(CO)3(PH3)] (M = Cr (3a), M = W (3b)) and [(CO)4W(μ-PH2)2W(CO)2(PH3)2] (4b) were isolated in moderate yield. Another synthetic approach to this type of compounds is the direct photolysis of the complexes [(CO)3M(PH3)3] (M = Cr (5a), M = W (5b)). The products were comprehensively characterized by 31P NMR and IR spectroscopy as well as by X-ray structural analysis. Additionally, the relevancy of 2a as single source precursor for the synthesis of stoichiometry-controlled CrP nanoparticles has been demonstrated.

Domaines: Chimie

Susanne Bauer, Cornelia Hunger, Michael Bodensteiner, Wilfried-Solo Ojo, Arnaud Cros-Gagneux, et al.. Transition-Metal Complexes Containing Parent Phosphine or Phosphinyl Ligands and Their Use as Precursors for Phosphide Nanoparticles. Inorganic Chemistry, 2014, 53 (21), pp.11438-11446. ⟨hal-02023190⟩