- Mono- and dinuclear germapalladacycles obtained via the Ge-Ge bond forming reactions promoted by palladium complexes
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Heating a toluene solution of bis(germyl)palladium complex [Pd(GeHPh 2)2(dmpe)] (2) (dmpe = 1,2-bis(dimethylphosphino)ethane) at 70 °C produced a mixture of dipalladium complexes, one with bridging digermene and germylene ligands, [{Pd(dmpe)}2(μ-GePh 2)(μ-Ge2Ph4)] (3), and also a mononuclear tetragermapalladacyclopentane, [Pd(GePh2GePh2GePh 2GePh2)(dmpe)] (4), in 92:8 molar ratio, respectively. The reaction of H2GePh2 with 2 in 10:1 molar ratio formed complex 4 as the main product (3:4 = 4:96). Complexes 3 and 4 were isolated from the above reactions and characterized by X-ray crystallography and NMR spectroscopy. Complex 3 reacted with H2GePh2 (Pd:Ge = 1:10) at 80 °C to yield 4 quantitatively, whereas simple heating of 3 at the same temperature did not form 4 at all. Reaction pathways for the Ge-Ge bond formation are discussed.
- Tanabe, Makoto,Ishikawa, Naoko,Hanzawa, Masaya,Osakada, Kohtaro
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- A triangular triplatinum(0) complex with bridging germylene ligands: Insertion of alkynes into the Pt-Ge bond rather than the Pt-Pt bond
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A new triangular triplatinum(0) complex with bridging diphenylgermylene ligands, [{Pt(PMe3)}3(μ-GePh2)3], undergoes insertion of ZCCZ (Z = COOMe) into a Pt-Ge bond. The product contains a μ3-η2(∥)-CZCZ-GePh2 ligand on the Pt3 plane. Two molecules of HCCZ react to afford the Pt3 complex with chelating C, Ge- and Ge, Ge-ligands. the Partner Organisations 2014.
- Tanabe, Makoto,Tanaka, Kimiya,Omine, Shumpei,Osakada, Kohtaro
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- Selective Synthesis and Derivatization of Germasilicon Hydrides
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Mixed Si/Ge hydrides SixGeyHz are valuable precursors for the deposition of binary Si-Ge alloys. This work describes the synthesis and full characterization of the previously unknown germaisotetrasilane Ph3GeSi(SiH3)3 (2) on a multigram scale from the reaction of the lithium silanide LiSi(SiH3)3 with Ph3GeCl. The stability of the Si-Ge bond in 2 versus electrophiles and nucleophiles has been investigated with the primary aim of developing new approaches to mixed sila-H-germanes (H3Ge)xSi(SiH3)4-x. With 1 equiv of MeLi, 2 reacted cleanly under cleavage of one Si-Si bond to give Ph3GeSi(SiH3)2Li, which is a valuable synthon for further derivatization. In contrast, the dephenylation reaction of 2 with 1 or 2 equiv of CF3SO3H/iBu2AlH proceeded much less selectively and afforded the desired Ph/H-germasilanes Ph2HGeSi(SiH3)3 and PhH2GeSi(SiH3)3 along with considerable amounts of Si-Ge scission products.
- Stueger, Harald,Christopoulos, Viktor,Temmel, Andrea,Haas, Michael,Fischer, Roland,Torvisco, Ana,Wunnicke, Odo,Traut, Stephan,Martens, Susanne
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- Gold(I) complexes with chloro(diaryl)silyl ligand. Stoichiometric reactions and catalysis for O-functionalization of organosilane
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An Au(I) complex with a chloro(diphenyl)silyl ligand [Au(SiPh2Cl)(PCy3)] (1a) is obtained from the reaction of Ph2SiH2 with [AuCl(PCy3)]. (4-FC6H4)2SiH2, (4-MeC6H4)2SiH2, and Ph2GeH2 react with [AuCl(PCy3)] to form complexes with the chlorodiarylsilyl ligand, [Au(SiAr2Cl)(PCy3)] (1b: Ar = C6H4-4-F, 1c: Ar = C6H4-4-Me) and with the chloro(diphenyl)germyl ligand, [Au(GePh2Cl)(PCy3)] (2a), respectively. Complex 1a reacts with H2O to form Ph2SiH(OH) and (Ph2SiH)2O, whereas the reaction of EtOH with 1a yields Ph2SiH(OEt) exclusively. Complex 1a catalyzes the hydrolysis of Ph2SiH2 ([Au]:[H2SiPh2]:[H2O] = 0.05:1.0:10.0) at 60 °C to yield Ph2SiH(OH) and (Ph2SiH)2O. The reaction of Ph2SiH2 with HOEt in the presence of a catalytic amount of 1a affords Ph2SiH(OEt). Both stoichiometric and catalytic reactions using 1a lead to the recovery of [AuCl(PCy3)] from the reaction mixture.
- Kanda, Atsushi,Osakada, Kohtaro,Tsuchido, Yoshitaka
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- Chromium carbonyl complexes with aryl mono- and oligogermanes: Ability for haptotropic rearrangement
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The intra- and intermolecular inter-ring η6 ? η6-haptotropic rearrangements (IRHR), occurring by involving interactions to Ge atoms in arylgermanes, were investigated theoretically and experimentally. The new methods for the synthesis of non-symmetrical polyaromatic Ge compounds were elaborated. Digermane Ph3GeGeMe2Cl (2) was obtained from Ph3GeGeMe2NMe2 (1) under action of Me3SiCl. Aryl digermane Ph3GeGeMe2(η6-C6H5)Cr(CO)3 (4) was obtained after lithiation of (η6-C6H6)Cr(CO)3 (3) with subsequent interaction with 2. It was established that thermally induced intramolecular IRHR in 4 is not observed experimentally; at similar reaction conditions in the presence of tetralin C10H12 (7) the bimolecular intermolecular IRHR occurs giving (η6-C10H12)Cr(CO)3 (8). DFT analysis of the intramolecular IRHRs for model germane (p-Tol)2Ge(H)(η6-Tol-p)Cr(CO)3 (MC1) and digermane Ph3GeGeH2(η6-C6H5)Cr(CO)3 (MC2) indicates a plausible effect of 3c-2e (agostic) Ge–H···Cr interaction on success of such rearrangement. The theoretical activation barrier is determined to be in the range of 35–37 kcal/mol. The model compound (η6-C6H3(GeHPh2)Me2-p)Cr(CO)3 (12) was obtained from (η6-C6H4Me2-p)Cr(CO)3 (11). The decomposition of 12 was observed under conditions of thermally induced IRHR. Molecular structures of 8, 11 and 12 in a crystal were investigated by XRD.
- Zaitsev, Kirill V.,Gloriozov, Igor P.,Oprunenko, Yuri F.,Lermontova, Elmira Kh,Churakov, Andrei V.
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p. 217 - 227
(2019/10/16)
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- Bond formation and coupling between germyl and bridging germylene ligands in dinuclear palladium(I) complexes
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The dinuclear palladium(I) complexes [L-(Ar2HGe)Pd(μ-GeAr2)2Pd(GeHAr2)L] (Ar = Ph, p-Tol; L= PMe3, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge...Ge bond lengths of 2.8263(4) ? (L = PMe3) and 2.928(1) ? (L = tBuNC), which are close to the longest Ge-Ge bond reported to date [2.714(1) ?]. Significant Ge...Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge...Ge interaction, and simultaneously activates two Pd-Ge bonds. Adding the chelating diphosphine 1,2-bis(diethylphosphino)-ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.
- Tanabe, Makoto,Omine, Shumpei,Ishikawa, Naoko,Osakada, Kohtaro,Hayashi, Yoshihiro,Kawauchi, Susumu
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supporting information
p. 2679 - 2683
(2015/03/04)
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- Germyl- and germylene-bridged complexes of Rh/Ir and subsequent chemistry of a bridging germylene group
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A series of neutral and cationic germylene-bridged complexes and a neutral germyl(germylene) complex have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Reaction of 1 equiv of primary germanes, RGeH3 (R = Ph, tBu), with [RhIr(CO)3(dppm) 2] (1) at low-temperature yields [RhIr(GeH2R)(H)(CO) 3(dppm)2] (R = Ph (3) or tBu (4)), the products of single Ge-H bond activation, which upon warming transform to the germylene-bridged dihydrides, [RhIr(H)2(CO)2(μ-GeHR) (dppm)2] (R = Ph (5) or tBu (6)) by activation of a second Ge-H bond accompanied by CO loss. Both classes of compounds have the diphosphines folded back in a "cradle-shaped" geometry. Although compound 5 reacts with additional phenylgermane at -40 °C to give a germylene-bridged/germyl product, [RhIr(GeH2Ph)(H) 2(CO)2(κ1-dppm)(μ-GeHPh)(μ-H)(dppm) ] (7), warming results in decomposition. However, reaction of 5 with 1 equiv of diphenylgermane at ambient temperature results in a novel mixed bis(μ-germylene) complex, [RhIr(CO)2(μ-GeHPh)(μ-GePh 2)(dppm)2] (8), containing both mono- and disubstituted germylene fragments. Reaction of 1 equiv of diphenylgermane with complex 1 produces a similar monogermylene-bridged product, [RhIr(H)2(CO) 2(μ-GePh2)(dppm)2] (9), while reaction of 1 with 2 equiv of diphenylgermane yields the germyl/germylene product [RhIr(H)(GeHPh2)(CO)3(κ1-dppm)(μ- GePh2)(dppm)] (10). The above reactions, incorporating first one and then a second equivalent of primary and secondary germanes, were studied by low-temperature multinuclear NMR spectroscopy, revealing details about the stepwise activations of multiple Ge-H bonds. Reaction of diphenylgermane with the cationic complex [RhIr(CH3)(CO)2(dppm) 2][CF3SO3] (2) leads to a cationic A-frame-type germylene- and hydride-bridged product, [RhIr(CO)2(μ-H)(μ- GePh2)(dppm)2][CF3SO3] (3), which reversibly activates H2, yielding a germyl-bridged dihydride and reacts stoichiometrically with water, methanol, and HCl to yield the respective germanol, germamethoxy, and germylchloride products.
- Mobarok, Md Hosnay,McDonald, Robert,Ferguson, Michael J.,Cowie, Martin
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p. 4020 - 4034
(2012/05/31)
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- Chemical properties of tetragermaplatinacyclopentane. Insertion of an alkyne into a Pt-Ge bond and silylation caused by H2SiPh2
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A platinum complex having dibutylgermyl ligands, [Pt(GeHBu 2)2(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane), reacted with excess H2GeBu2 at 90 °C to yield a five-membered tetragermaplatinacycle, [Pt(GeBu2GeBu 2GeBu2GeBu2)(dmpe)] (6). The direct reaction of H2GeBu2 with [Pt(dmpe)2] in 5:1 ratio also gave 6 in 67% yield. The reaction of dimethyl acetylenedicarboxylate with 6 caused insertion of a C≡C bond into a Pt-Ge bond to form a seven-membered germaplatinacycloheptene, which was characterized by X-ray crystallography. Complex 6 reacted with H2GePh2 and H2SiPh 2 in 1:2 ratio to produce a mixture of tetragermane dihydride H(GeBu2)4H and bis(silyl)- or bis(germyl)platinum complexes [Pt(EHPh2)2(dmpe)] (E = Si, Ge).
- Tanabe, Makoto,Deguchi, Takashi,Osakada, Kohtaro
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p. 3386 - 3391
(2011/08/06)
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- ETUDE DE NOUVELLES REACTIONS PAR TRANSFERT MONOELECTRONIQUE: ACTION D'ORGANOGERMYLLITHIUMS SUR LE FURFURAL, LE THIOPHENALDEHYDE ET LES DERIVES NITRES CORRESPONDANTS
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The organogermyllithiums R3GeLi (R=Ph, Mes) were treated with several carbonyl conjugated substrates (2-furaldehyde, 2-thiophenecarboxaldehyde and their nitro-corresponding compounds).Only the germylation reactions of carbonyl group have been observed with a regioselectivity depending on the nature of the insaturated cycle.With 2-furaldehyde and 2-thiophenecarboxaldehyde, the germylcarbinols 1 are mainly obtained by C-germylation reaction.When an excess of aldehyde was used, the formation of germylketone 2 is surprisingly observed.With nitro compounds, the O-germylation reaction is preponderant.In this case, a single electron transfer mechanism takes place and was confirmed by ESR study.We observed the corresponding organic radical anion.The hyperfine structure of which has been resolved.Key words: SET reactions, germylation, radical anion, germyllithiums, germylketones, germanium centered radical.
- Riviere, P.,Castel, A.,Cosledan, F.
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p. 169 - 180
(2007/10/02)
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- Complexes du fer hydro-digermanies: 5-C5H5)(CO)2> (R = Et, Ph) - etude photolytique
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The new complexes 5-C5H5)(CO)2> (R=Et or Ph) were prepared by a substitution reaction from the corresponding arylhalohydrodigermanes and the iron salt.Their characterization by IR, 1H and 13C NMR and mass spectroscopy is reported.Photolysis of each complex affords transient monohydrogermylcomplexes 5-C5H5)(CO)2> and dialkylgermylenes which are trapped by 3,5-di-tert-butylorthoquinone and dimethyldisulphide with correct yields.These photolytic reactions are not affected by radical initiators like peroxide.
- Castel, A.,Riviere, P.,Ahbala, M.,Satge, J.,Soufiaoui, M.,Knouzi, N.
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p. 123 - 130
(2007/10/02)
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- Nouveaux aryldihydrogermyllithium
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The new aryldihydrogermyllithium complexes RH2GeLi (R = Ph, Mes) are prepared, in good yields, by metallation of the parent trihydrogermane with t-butyllithium in THF.They are characterized by alkylation reactions with MeI.Some germylation reactions are reported: they lead to the formation of new functional aryldihydrogermanes and aryldigermanes by a nucleophilic substitution.These aryldihydrogermyllithium complexes react also with acyl chlorides RCOCl (R = Ph, Mes) to give new diacyl- and triacyl-germanes.These easily add to the carbonyl group of aromatic aldehydes, thereby giving the corresponding α-germyl alcohols.
- Castel, A.,Riviere, P.,Satge, J.,Desor, D.
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- The Ge-H bond dissociation energies of organogermanes. A laser-induced photoacoustic study
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The Ge-H bond dissociation energies (BDE's) of several alkyl- and aryl-substituted germanium hydrides have been measured in hydrocarbon solution at room temperature by a photoacoustic technique. The BDE's of these hydrides are unaffected by alkyl substitution when compared to those for GeH4 and are in the range of 81.6-82.6 kcal/mol. Aryl substitution leads to a slightly weakened Ge-H bond (79.2-80.2 kcal/mol) in the cases of phenyl-, diphenyl-, and triphenylgermane. In an effort to further characterize the formation, spectral and decay properties of the germyl radicals some laser flash photolysis studies were carried out. The rate constants for hydrogen abstraction by tert-butoxy radicals were determined by nanosecond laser flash photolysis and fell in the range (0.7-4.4) × 108 M-1 s-1. The aryl-substituted germyl radicals add to the aromatic rings of the germane precursor. Diphenylgermyl radical adds to diphenylgermane with a rate constant of 2.9 × 105 M-1 s-1, while phenylgermyl radical adds to phenylgermane with a rate constant of 1.2 × 106 M-1 s-1.
- Clark, K. Brady,Griller, David
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p. 746 - 750
(2008/10/08)
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- New (diarylgermyl)lithiums
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The new (diarylgermyl)lithiums R2GeHLi (2; R = phenyl, mesityl) were prepared in good yields by hydrogermolysis reactions of tert-butyllithium in THF. The stability of compounds 2 depends on the nature of the R group and the solvent. For R = Ph, in the presence of an amine (Et3N or Et2NMe), the same reaction leads to the formation of the polygermanes H(GePh2)nH (n = 2-4). The characterization of compounds 2 by IR and 1H and 13C NMR spectroscopy and their complexation with a crown ether are also reported. They are characterized by deuterolysis and alkylation reaction (with MeI and Me2SO4). Their germylation reactions with Ge-Cl reagents constitute a convenient way for synthesizing organo-hydropolygermanes. Compounds 2 also react with acyl chlorides to give new germyl ketones, R2HGeCOR′, and the unexpectedly stable β-germyl diketone Ph2Ge(COMes)2.
- Castel,Riviere,Satge,Ko
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p. 205 - 210
(2008/10/08)
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- Arylhydrogermyllithiums: synthese et applications
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New organohydrogermyllithium are prepared in good yields from hydrogermolysis reactions with t-butyllithium in THF.Alkylation and germylation of the germanium-lithium bond in these compounds are efficient reactions and a convenient way for synthesis of organohydropolygermanes.These reagents are also useful for the formation of unknown hydrogermylmagnesium compounds.
- Castel, Annie,Riviere, Pierre,Satge, Jacques,Ko, Young-Hoon
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- Preparation and Some Reactions of Diarylgermylenedialkali Metals
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The reactions of diarylgermanes with alkali metals in HMPA/THF or THF were found to give the corresponding diarylgermylenedialkali metals in high yields.Diphenylgermylenedipotassium reacted with aryl halides or carbonyl compounds to give reduction products predominantly.With alkyl halides, diphenylgermylenedipotassium gave mainly substitution products.
- Mochida, Kunio,Matsushige, Naoki,Hamashima, Mari
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p. 1443 - 1447
(2007/10/02)
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- ASSISTANCE NUCLEOPHILE DANS DES REACTIONS D'ORGANO-HALOGENO- ET -HALOGENO-HYDROGERMANES: GERMYLANIONS, GERMYLENES, DERIVES FONCTIONNELS DU GERMANIUM
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Substitution reactions of halogermanes under nucleophilic assistance of tertiary amines or diazo derivatives leading readily to various functional derivatives of germanium have been carried out.Dehydrohalogenation of acidic halohydrogemanes under nucleophilic assistance is a useful way to divalent species, and the germylenes formed are stabilized by complexation with the nucleophilic agent.The reactions proceed via intermediate halogermylanions which lead to the formation of more stable germylenes.The transient halogemylanions have been characterized by means of their nuclophilic additions to carbonyl derivatives.Nucleophilic substitutions of halogermanes using these germylanions lead to the formation of polygermanes.
- Riviere, P.,Castel, A.,Satge, J.
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p. 123 - 136
(2007/10/02)
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- ASSISTANCE NUCLEOPHILE DANS DES REACTIONS DE REDUCTION D'ORGANOHALOGENO- ET HALOGENO-GERMANES PAR DES REDUCTEURS DOUX R3M(IVB)-H ET RCHO: GERMYLANIONS, DERIVES FONCTIONNELS DU GERMANIUM
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Catalytic activity of nuclophiles such as tertiary amines and diazo derivatives in the reduction of halogermanes by means of gentle reductive agents, such as R3M(IVB)-H or RCHO, has been shown.In the particular case of enolisable aldehyde, a competition between nucleophilic substitution at the metal and germanium-halogen bond reduction has been observed.Transposition of enoxygermanes formed through the substitution process, leads to β-germylaldehydes.
- Castel, A.,Riviere, P.,Satge, J.
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p. 137 - 146
(2007/10/02)
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- THE CHEMICAL BEHAVIOUR OF COBALT-STABILIZED-CARBENES HAVING A TRISUBSTITUTED SILYL OR GERMYL LIGAND. STEREOSPECIFIC FORMATION OF BENZOYLSILANES FROM THE REACTION OF ORGANOSILYL-COBALT TETRACARBONYL DERIVATIVES WITH PHENYLLITHIUM
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We report the chemical behaviour of cobalt-stabilized carbenes, R3M(CO)3CoC(OEt)R', and their parent anions, R3M(CO)3CoC(O-)R', where M = Si or Ge.The anions where M = Si, R' = Ph decompose thermally into the corresponding benzoylsilanes; when the silicon atom is chiral (R3 = MePh-1-Np) optically active R3SiCOPh is obtained with complete retention of configuration.
- Cerveau, Genevieve,Colomer, Ernesto,Corriu, Robert J.P.,Young, J. Colin
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