title: Transition-metal complexes containing parent phosphine or phosphinyl ligands and their use as precursors for phosphide nanoparticles.
abstract: 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)(x)M(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 (31)P 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.
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg , Universitätsstrasse 31, Regensburg, D-93053 Germany.
authors.forename: Susanne
authors.initials: S
authors.lastname: Bauer
authors.forename: Cornelia
authors.initials: C
authors.lastname: Hunger
authors.forename: Michael
authors.initials: M
authors.lastname: Bodensteiner
authors.forename: Wilfried-Solo
authors.initials: WS
authors.lastname: Ojo
authors.forename: Arnaud
authors.initials: A
authors.lastname: Cros-Gagneux
authors.forename: Bruno
authors.initials: B
authors.lastname: Chaudret
authors.forename: Céline
authors.initials: C
authors.lastname: Nayral
authors.forename: Fabien
authors.initials: F
authors.lastname: Delpech
authors.forename: Manfred
authors.initials: M
authors.lastname: Scheer