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'Al'l about F: Aluminum chlorofluoride (ACF) catalyzes the hydrodefluorination, as well as Friedel–Crafts reactions of fluorinated methanes in the presence of Et3SiH. A surface‐bound silylium‐ion‐like species is considered to be a crucial intermediate in achieving the CF bond cleavage.

The activation of SF at [Pt(PR ) ] R=Cy, iPr complexes in the presence of PR led selectively and in an unprecedented reaction route to the generation of the SF complexes trans-[Pt(F)(SF )(PR ) ]. These can also be synthesized from SF and the SF derivative trans-[Pt(F)(SF )(PCy ) ][BF ] was characterized by X-ray crystallography. trans-[Pt(F)(SF )(PR ) ] complexes are useful tools for deoxyfluorination reactions and novel fluorido complexes bearing a SOF ligand are formed. Based on these studies a process for the deoxyfluorination of ketones was developed with SF as fluorinating agent.

In this work, we present a mild method for direct conversion of primary alcohols into carboxylic acids with the use of water as an oxygen source. Applying a ruthenium dihydrogen based dehydrogenation catalyst for this cause, we investigated the effect of water on the catalytic dehydrogenation process of alcohols. Using 1 mol% of the catalyst we report up to high yields. Moreover, we isolated key intermediates which most likely play a role in the catalytic cycle. One of the intermediates was identified as a trans dihydrido carbonyl complex which is generated in situ in the catalytic process.

The reaction of [PtCl 2 (COD)] (COD = 1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr 2 P-(C 9 H 8 N)) led to the formation of the platinum(ii) chlorido complexes, cis-[PtCl 2 {iPr 2 P(C 9 H 8 N)} 2 ] (1) and trans-[PtCl 2 {iPr 2 P-(C 9 H 8 N)} 2 ] (2). The cis-complex 1 reacted with NEt 3 yielding the complex cis-[PtCl{k 2 -(P,N)-iPr 2 P(C 9 H 7 N)}{iPr 2 P(C 9 H 8 N)}] (3) bearing a cyclometalated k 2 -(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt 3 . Treatment of 1 or 3 with (CH 3 ) 4 NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{k 2 -(P,N)-iPr 2 P(C 9 H 7 N)} 2 ] (4). The molecular structures of the complexes 1-4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF {k 2 -(P,N)-iPr 2 P(C 9 H 7 N)}{iPr 2 P(C 9 H 8 N)}] • (HF) 4(5 • (HF) 4 ) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii) fluorido complex 5 • (HF) 4 exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3, complex 5 • (HF) 4 reacted with CO or the ynamide 1-(2phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){k 2 -(P,C)-iPr 2 P(C 9 H 7 NCO)}{iPr 2 P(C 9 H 8 N)}][F(HF) 4 ] (7) and a complex, which we suggest to be cis-[Pt{C = C(Ph)OCN(C 3 H 6 )} {k 2 -(P,N)-iPr 2 P(C 9 H 7 N)}{iPr 2 P(C 9 H 8 N)}][F(HF) 4 ] ( 9), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9.

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.

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The reaction of [Rh(H)(PEt 3 ) 3 ]( 1)w ith the refrigerant HFO-1234yf (2,3,3,3-tetrafluoropropene) affords an efficient route to obtain [Rh(F)(PEt 3 ) 3 ]( 3)b yC À Fb ond activation. Catalytic hydrodefluorinations were achieved in the presence of the silane HSiPh 3 .Inthe presence of afluorosilane, 3 provides aC ÀHb ond activation followed by a1 ,2-fluorine shift to produce [Rh{(E)-C(CF 3 )=CHF}(PEt 3 ) 3 ]( 4). Similar rearrangements of HFO-1234yf were observed at [Rh(E)-(PEt 3 ) 3 ][E= Bpin (6), C 7 D 7 (8), Me (9)].The ability to favor C À Hb ond activation using 3 and fluorosilane is also demonstrated with 3,3,3-trifluoropropene.S tudies are supported by DFT calculations.