Syntheses and structures of the tetra-phosphine complexes trans-MCl2(PH3)4 (M = Ru, Os)

Abstract

The air stable tetra-phosphine complexes trans-MCl(2)(PH(3))(4) (M = Ru, Os) are formed in high yield from reactions of MCl(3).3H(2)O with PH(3) in MeOH.

General and Selective Copper-Catalyzed Reduction of Tertiary and Secondary Phosphine Oxides: Convenient Synthesis of Phosphines

“…Here, no special handling and precautions are needed. It should be noted that this methodology could also be applied for reactions which involve primary phosphines …”

Iron, ruthenium and osmium

“…45 In the presence of the strong base KO t Bu, [Fe II (TMCS)] + reacts with the peracid m-CPBA forming [Fe IV (O)(TMCS)] + ; in the absence of base, an O-bound iron(II)-sulfinate complex is the first product, which on addition of more m-CPBA is converted into an iron(IV)-oxo sulfinate complex. 57 Among phosphine complexes, the dinitrogen- 62 Applications of iron complexes continue to hold out real promise in synthetic organic chemistry. 47 QO group; the change in spin state to high-spin; and the concentration of the oxidising power on one iron atom.…”

“…58 The tetradentate ligands (SiP 3 )Fe(NAr)]. 60 The chlorine-bridged dimer [( t SiP 3 )Fe(m-Cl) 3 Fe( t SiP 3 )] Cl can be cleaved 61 62 Applications of iron complexes continue to hold out real promise in synthetic organic chemistry. The complex [Fe((S,S)-PDP)(MeCN) 2 ] 2+ , which was recently shown to catalyse the stereospecific oxidation of unactivated tertiary C-H bonds by H 2 O 2 /CH 3 COOH, has now been shown to carry out site-selective oxidation of secondary C-H bonds to afford mono-oxygenated products in useful yield, with the sites oxidised being different to those chosen by enzymes.…”

Taming PH3: State of the Art and Future Directions in Synthesis

“…For example, Jones and coworkers reported the formation and isolation of a remarkably air-stable trans-[RuCl 2 (PH 3 ) 4 ] complex. 16 However, further study into reactivity with these complexes has rarely been explored 17 and will therefore not be the focus of this perspective. However, this highlights the many seemingly simple areas of PH 3 research that are yet to be fully investigated.…”

“…We would be remiss not to briefly mention the numerous reports, during a prolific period of PH 3 research that took place between the late 1960s through to the early 1990s, on the reaction between PH 3 and transition metal (TM) complexes. − Formation of TM complexes bearing the [TM]–PH 3 motif as well as formal oxidative addition/hydride abstraction to form [TM]–PH 2 and [TM]–(μ-PH 2 ) motifs have been identified, with analysis ranging from multinuclear NMR and IR data only, through to those also reporting single crystal X-ray diffraction data. For example, Jones and co-workers reported the formation and isolation of a remarkably air-stable trans -[RuCl 2 (PH 3 ) 4 ] complex . However, further study into reactivity with these complexes has rarely been explored and will therefore not be the focus of this perspective.…”