No abstract

The reaction of the silyl complex [Rh{Si(OEt)}(PEt)] (1) with 3,3,3-trifluoropropene afforded the rhodium complex [Rh(CHCHCF){Si(OEt)}(PEt)] (2) which features a bonded fluorinated olefin. In contrast the rhodium hydrido complex [Rh(H)(PEt)] (3) yielded on treatment with 3,3,3-trifluoropropene in the presence of a base the fluorido complex [Rh(F)(PEt)] (4) together with 1,1-difluoro-1-propene by C-F bond activation. At low temperature the intermediate fac-[Rh(H)(CHCHCF)(PEt)] (5) was detected by NMR spectroscopy. The germyl complex [Rh(GePh)(PEt)] (6) reacted also with 3,3,3-trifluoropropene by C-F bond activation affording again the fluorido complex [Rh(F)(PEt)] (4) as well as the (3,3-difluoroallyl)triphenylgermane 7. The catalytic hydrogermylation of 3,3,3-trifluoropropene in the presence of various germanium hydrides under mild conditions was developed by employing complex 6 as a catalyst. The molecular structures of both germane derivatives (3,3-difluoroallyl)triphenylgermane 7 and 1,1,1-trifluoropropane-3-triphenylgermane 8 were determined by X-ray crystallography.

The bissilyl complexes 3–6 were synthesized by reactions of the platinum(0) complexes [Pt(η2‐C2H4)(diphos)] (1: diphos = dppe; 2: diphos = dcpe) with the disilanes 1, 1,2, 2‐tetramethyldisilane and 1, 1,2, 2‐tetraphenyldisilane via Si–Si bond activation. The molecular structures of 4 and 5 in the solid state are reported. The reaction of 2 with HPh2SiSiPh2H led to the immediate formation of the hydrido disilanyl complex [Pt(H)(SiPh2SiPh2H)(dcpe)] (7), which converts slowly into the bissilyl complex [Pt(SiHPh2)2(dcpe)] (6). The latter was reported before to be a η2‐disilene complex.

Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF led to a variety of fluorido and fluorovinyl complexes.

The activation of tetrafluoropropenes at rhodium silyl and germyl complexes revealed various reaction pathways such as the generation of organic derivatives of the substrate and a rhodium fluorido complex or the formation of rhodium vinyl complexes.