The activation of CO2, CS2 as well as of PhNCO at [Rh(Bpin)(PEt3)3] led to C=X bond cleavage and the formation of {RhXBpin} species (X = O, S, N). Treatment of the boryl complex [Rh(Bpin)(PEt3)3] with 0.5 equivalents of CS2 resulted in the fragmentation of CS2 and the formation of the remarkable μ-carbido complex trans-[Rh2(μ-C)(SBpin)2(PEt3)4].
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.
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.
As a rather inert gas, sulfur hexafluoride is still used as a dielectric in high-voltage power applications despite its high global warming potential. Its activation at transition metal complexes has been reported, but the fate of the sulfur-containing products is often unknown. The activation of SF 6 at [Rh(H){ tBu xanPOP}] ( tBu xanPOP = 9,9-dimethyl-4,5-bis(ditertbutylphosphino)xanthene) at room temperature leads to the generation of the bifluorido complex [Rh(FHF){ tBu xanPOP}]. A subsequent regeneration of [Rh(H){ tBu xanPOP}] completes a cyclic process for the degradation of SF 6 . Furthermore, the SF 6 activation at [Rh(H){ tBu xanPOP}] in the presence of triethylsilane as a hydrogen source is described, which leads to the formation of the fluorido complex [Rh(F) 2 (H){ tBu xanPOP}] as well as [Rh(SH)-{ tBu xanPOP}] and S(SiEt 3 ) 2 as sulfur-containing products.
The sterically demanding β‐diketiminate ligand Ldmp [Ldmp = HC{(CMe)N(dmp)}2, dmp = C6H3‐2,6‐Me2] was used to stabilize various gallium complexes in the formal oxidation states +II and +III. The reaction of in situ generated [LdmpLi] with gallium chloride affords [LdmpGaCl2] (1), which was used as starting complex to synthesize a variety of gallium(III) compounds [LdmpGaX2] [X = F (2), I (3), H (4), and Me (5)]. Synthesis of the dinuclear complex [LdmpGaI]2 (6), with gallium in the formal oxidation state +II was accomplished by converting “GaI” with in situ generated [LdmpLi] in toluene. All compounds were characterized by elemental analyses, NMR spectroscopy, LIFDI‐TOF‐MS, and single‐crystal X‐ray diffraction. Additionally DFT calculations were performed for analysis of the bonding in 6.
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