Ruthenium‐Catalyzed Oxidation of Alkenes,Alkynes, and Alcohols to Organic Acids with Aqueous Hydrogen Peroxide

A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me₃tacn)(CF₃CO₂)₂Ru^III(OH₂)]CF₃CO₂ ( 1 ; Me₃tacn=1,4,7‐trimethyl‐1,4,7‐triazacyclononane) as a catalyst for oxidation of alkenes, alkynes, and alcohols to organic acids in over 80 % yield is presented. For the oxidation of cyclohexene to adipic acid, the loading of 1 can be lowered to 0.1 mol %. On the one‐mole scale, the oxidation of cyclohexene, cyclooctene, and 1‐octanol with 1 mol % of 1 produced adipic acid (124 g, 85 % yield), suberic acid (158 g, 91 % yield), and 1‐octanoic acid (129 g, 90 % yield), respectively. The oxidative C?C bond‐cleavage reaction proceeded through the formation of cis‐ and trans‐diol intermediates, which were further oxidized to carboxylic acids via C? C bond cleavage.     

Versatile Conversion of N‐Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal–Carbon and Metal–Hydrogen Bonds

The facile one‐pot reaction of the stable N‐heterocyclic silylene LSi: 1 (L?(ArN)C(?CH₂) CH?C(Me)(NAr), Ar=2,6‐iPr₂C₆H₃) with Me₂Zn, Me₃Al, H₃Al‐NMe₃, and MeLi has been investigated. The silicon(II) atom in 1 is capable of insertion into the corresponding M? C and Al? H bonds under very mild reaction conditions. Thus, Me₂Zn furnishes the bis(silyl) zinc complex LSi(Me)ZnSi(Me)L 2 as the sole product, irrespective of the molar ratio of the starting materials applied. Moreover, the reactions of 1 with Me₃Al, H₃Al‐NMe₃, and MeLi lead directly to the 1,1‐addition products LSi(Me)(Al(thf)Me₂) 3 , LSi(H)(AlH₂(NMe₃)) 4 , and LSi(Me)Li(thf)₃ 5 , respectively. All new compounds 2 – 5 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single‐crystal X‐ray diffraction analyses.     

Gemischtligandkomplexe des Rheniums. IX. Reaktionen am Nitridoliganden von [ReN(Me2PhP)(Et2dtc)2]. Synthese,Charakterisierung und Kristallstrukturen von [Re(NBCl3)(Me2PhP)(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2] und [Re(NS)Cl(Me2PhP)2(Et2dtc)]

Mixed-ligand Complexes of Rhenium. IX. Reactions on the Nitrido Ligand of [ReN(Me₂PhP)(Et₂dtc)₂]. Synthesis, Characterization, and Structures of [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] BCl₃, GaCl₃ and S₂Cl₂ react with the well-known [ReN(Me₂PhP)(Et₂dtc)₂] by attack of the nucleophilic nitrido ligand. Final products of these reactions are [Re(NBCl₃)-(Me₂PhP)(Et₂dtc)₂], [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂], and [Re(NS)Cl(Me₂PhP)₂Et₂dtc)] which have been studied by mass spectrometry, IR spectroscopy and X-ray diffraction. [Re(NBCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in the triclinic space group P1 , Z = 2, a = 8.151(6), b = 9.935(8), c = 18.67(1) Å; α = 94.42(4), β = 97.09(1), γ = 101.35(4)°. The coordination geometry is a distorted octahedron. The equatorial coordination sphere is occupied by one phosphorus and three sulphur atoms. The fourth sulphur atom is in trans position to the Re?N? B moiety. The almost linear Re?N? B unit has an Re?N? B angle of 170.5(3)° with a Re? N bond length of 1.704(3) Å. The analogous [Re(NGaCl₃)(Me₂PhP)(Et₂dtc)₂] crystallizes in P2₁/c with a = 8.138(3), b = 18.279(2), c = 19.880(6) Å; β = 99.81(2)°; Z = 4. Rhenium has a distorted octahedral environment. The Re? N? Ga bond is slightly bent with an angle of 154.5(4)° and a Re? N bond length of 1.695(6) Å. [Re(NS)Cl(Me₂PhP)₂(Et₂dtc)] crystallizes in the triclinic space group P1 , Z = 4, a = 9.514(2); b = 16.266(5); c = 18.388(3) Å; α = 88.75(2), β = 76.59(2), γ = 85.50(2)° with two crystallographically independent molecules in the asymmetric unit. Rhenium has a distorted octahedral environment with the chloro ligand in trans position to the almost linear thionitrosyl group. The Re?N bond lengths are 1.795(6) and 1.72(1) Å, respectively, and the N?S distances are 1.55(1) and 1.59(1) Å, respectively.     

Gemischtligand-Komplexe des Rheniums. VI. Darstellung und Strukturen der Rhenium?Thionitrosyl-Komplexe mer-[Re(NS)Cl2(Me2PhP)3] · CH2Cl2 und trans-[Re(NS)Cl3(Me2PhP)2]

Mixed-ligand Complexes of Rhenium. VI. Synthesis and X-Ray Structures of the Rhenium Thionitrosyl Complexes mer-[Re(NS)Cl₂(Me₂PhP)₃] · CH₂Cl₂ and trans-[Re(NS)Cl₃(Me₂PhP)₂] mer-Dichlorotris(dimethylphenylphosphine)(thionitrosyl)rhenium(I), mer-[Re(NS)Cl₂(Me₂PhP)₃], and trans-Trichlorobis(dimethylphenylphosphine)(thionitrosyl)rhenium(II), trans-[Re(NS)Cl₃(Me₂PhP)₂], are formed during the reaction of rhenium(V) mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] with disulphur dichloride (HR₂tcb = N-(N,N-dialkylthiocarbamoyl)benzamidine). The chelating ligands are substituted during the reaction. mer-[Re(NS)Cl₂(Me₂PhP)₃] crystallizes monoclinic in the space group P2₁/n. The dimensions of the unit cell are a = 8.854(2); b = 31.295(3); c = 11.981(3) Å; β = 108.14(1)°; Z = 4. A final R value of 0.033 was achieved on the basis of 5 387 reflections with I ≥ 3σ(I). The rhenium atom is coordinated in a distorted octahedral environment. The Me₂PhP ligands are arranged meridionally cis to the linear thionitrosyl group. trans-[Re(NS)Cl₃(Me₂PhP)₂] crystallizes in the monoclinic space group C2/c with an unit cell of the dimensions a = 33.320(9); b = 8.446(1); c = 17.28(5) Å; β = 116.09(1)°, Z = 8. The R value converged at 0.026 on the basis of 5 460 independent reflections. The metal is octahedrally coordinated with the phosphine ligands in trans position to each other. The angle Re? N? S is 175.7(3)°.     

Gemischtligandkomplexe des Technetiums. XV. Zur Reaktion von [TcNCl2(Me2PhP)3] mit Dialkyldithiocarbamaten und N,N-Dialkylthiocarbamoylbenzamidinen

Mixed-ligand Complexes of Technetium. XV. The Reaction of [TcNCl₂(Me₂PhP)₃] with Dialkyldithiocarbamates and N,N-Dialkylthio-carbamoylbenzamidines [TcN(Cl)(Me₂PhP)₂(Et₂dtc)], [TcN(Me₂PhP)(Et₂dtc)₂], and [TcN(Et₂dtc)₂] can be prepared by stepwise ligand exchange reactions starting from dichlorotris(dimethylphenylphosphine)nitridotechnetium(V), [TcNCl₂(Me₂PhP)₃], and diethyldithiocarbamate. In contrast to this, only one intermediate, [TcN(Cl)(Me₂PhP)₂(HEt₂tcb)], could be isolated during the reaction with N,N-Diethlthiocarbamoylbenzamidine, which yields the bis chelate [TcN(HEt₂tcb)₂]. [TcN(Me₂PhP)(Et₂dtc)₂] crystallizes in the monoclinic space group P2₁/c; a = 17.369(5) Å, b = 15.024(1) Å, c = 9.906(3) Å, β = 76.47(1)º, Z = 4. The phosphine is coordinated equatorially. The multiply bonded nitrogen ligand (Tc? N(1) 1.624(3) Å) strongly labilizes the trans positioned donor atom (distance Tc? S(4) 2.826(1) Å). [TcN(HEt₂tcb)₂] crystallizes in the triclinic space group P1 with a = 9.749(4) Å, b = 11.264(4) Å, c = 12.359(4) Å, α = 75.34(2)º, β = 79.69(2)º, γ = 87.55(2)º, Z = 2. The metal is five-coordinate with the nitrido donor atom occupying the apex of a square pyramid. It's basal plane is formed by the cis-coordinated chelate ligands. The technetium is situated over the basal plane by about 0.6 Å. The Tc?N distane was found to be 1.610(5) Å.     

Soft Scorpionate Hydridotris(2-mercapto-1-methylimidazolyl) borate) Tungsten-Oxido and -Sulfido Complexes as Acetylene Hydratase Models

A series of W^IV alkyne complexes with the sulfur-rich ligand hydridotris(2-mercapto-1-methylimidazolyl) borate) (Tm^Me) are presented as bio-inspired models to elucidate the mechanism of the tungstoenzyme acetylene hydratase (AH). The mono- and/or bis-alkyne precursors were reacted with NaTm^Me and the resulting complexes [W(CO)(C₂R₂)(Tm^Me)Br] (R=H 1 , Me 2 ) oxidized to the target [WE(C₂R₂)(Tm^Me)Br] (E=O, R=H 4 , Me 5 ; E=S, R=H 6 , Me 7 ) using pyridine-N-oxide and methylthiirane. Halide abstraction with TlOTf in MeCN gave the cationic complexes [WE(C₂R₂)(MeCN)(Tm^Me)](OTf) (E=CO, R=H 10 , Me 11 ; E=O, R=H 12 , Me 13 ; E=S, R=H 14 , Me 15 ). Without MeCN, dinuclear complexes [W₂O(μ-O)(C₂Me₂)₂(Tm^Me)₂](OTf)₂ ( 8 ) and [W₂(μ-S)₂(C₂Me₂)(Tm^Me)₂](OTf)₂ ( 9 ) could be isolated showing distinct differences between the oxido and sulfido system with the latter exhibiting only one molecule of C₂Me₂. This provides evidence that a fine balance of the softness at W is important for acetylene coordination. Upon dissolving complex 8 in acetonitrile complex 13 is reconstituted in contrast to 9 . All complexes exhibit the desired stability toward water and the observed effective coordination of the scorpionate ligand avoids decomposition to disulfide, an often-occurring reaction in sulfur ligand chemistry. Hence, the data presented here point toward a mechanism with a direct coordination of acetylene in the active site and provide the basis for further model chemistry for acetylene hydratase.     

Stabilization of a Silaaldehyde by its η2 Coordination to Tungsten

Treatment of pyridine‐stabilized silylene complexes [(η⁵‐C₅Me₄R)(CO)₂(H)W?SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe₃)₃) with an N‐heterocyclic carbene ^MeIⁱPr (1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η⁵‐C₅Me₄R)(CO)₂W?SiH(Tsi)][H^MeIⁱPr] (R=Me ( 1‐Me ); R=Et ( 1‐Et )). Subsequent oxidation of 1‐Me and 1‐Et with pyridine‐N‐oxide (1 equiv) gave anionic η²‐silaaldehydetungsten complexes [(η⁵‐C₅Me₄R)(CO)₂W{η²‐O?SiH(Tsi)}][H^MeIⁱPr] (R=Me ( 2‐Me ); R=Et ( 2‐Et )). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis.     

Gemischtligand-Komplexe des Rheniums. IV. Die Reaktion von [ReNCl2(Me2PhP)3] mit Dithiocarbamaten. Kristallstrukturen von trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphan) nitridorhenium(V), [ReN(Cl)(Me2PhP)2(Me2dtc)], und Bis(diethyldithiocarbamato)(dimethylphenylphosphan)nitridorhenium(V), [ReN(Me2PhP)(Et2dtc)2]

Mixed-Ligand Complexes of Rhenium IV. The Reaction of [ReNCl₂(Me₂PhP)₃] with Dithiocarbamates. X-Ray Crystal Structures of trans-Chloro-dimethyldithiocarbamato-bis(dimethylphenylphosphine) nitridorhenium(V), [ReN(Cl)(Me₂PhP)₂(Me₂dtc)], and Bis(diethyldithiocarbamato)(dimethylphenylphosphine)nitridorhenium(V), [ReN(Cl)(Me₂PhP)(Et₂dtc)₂] [ReNCl₂(Me₂PhP)₃] reacts with dialkyldithiocarbamates, R₂dtc^?, under a stepwise ligand exchange. Final products of these reactions are the well-known [ReN(R₂dtc)₂] bischelates. Intermediatelly, however, complexes of the general formulae [ReN(Cl)(Me₂PhP)₂(R₂dtc)] and [ReN(Me₂PhP)(R₂dtc)₂] can be isolated. Representatives have been structurally characterized. [ReN(Cl)(Me₂PhP)₂(Me₂dtc)] crystallizes monoclinic in the space group P2₁/c, Z = 4. The dimensions of the unit cell are a = 13.071(3); b = 11.622(1); c = 15.667(3) Å; β = 97.09(1)°. The rhenium atom has a distorted octahedral environment; the Re≡N bond length is 1.71(1) Å. The Re? Cl bond distance is markedly lengthened (2.665(2) Å) as a consequence of the strong trans labilizing influence of the coordinated nitrido ligand. [ReN(Me₂PhP)(Et₂dtc)₂] crystallizes monoclinic in the space group P2₁/c, Z = 4, a = 17.262(3); b = 14.915(2); c = 9.888(2); β = 76.35(8)°. The equatorial coordination sphere is occupied by one phosphorus atom and three sulphur atoms. One of the dithiocarbamate ligands is coordinated bidentately; the second one with two distinct Re? S bond lengths. The Re? S(4) distance is 2.7983(2) Å which can be discussed as a weak interaction with the metal.     

Ruthenium(II) carbonyl complexes with N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives and triphenylphosphine as effective catalysts for oxidation of alcohols

Ruthenium(II) complexes, [RuCl(L)(CO)(PPh₃)₂] {where L?=?N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives}, are prepared from reaction between [RuHCl(CO)(PPh₃)₃] and N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives in toluene and characterized by elemental analysis and spectral data (electronic, infrared, ¹H NMR, and ³¹P NMR). The combination of [RuCl(L)(CO)(PPh₃)₂] (0.01?mmol) and N-methylmorpholine-N-oxide (NMO) (3?mmol) is an active catalyst for the oxidation of primary, secondary, cyclic, allylic, aliphatic, and benzylic alcohols to their corresponding aldehydes and ketones at room temperature. The oxidation protocol is simple to operate and gives the corresponding carbonyl compounds good to excellent yields.     

Enantioselective Reduction of Prochiral Ketones with NaBH4/Me2SO4/(S)-Me-CBS

The enantioselective reduction of prochiral ketones with NaBH₄/Me₂SO₄/(S)-Me-CBS is described. Borane is generated in situ via the reaction of NaBH₄ with Me₂SO₄ in tetrahydrofuran, which is as efficient as the commercial one. Such in situ–generated borane reagent was applied to reduce prochiral ketones in the presence of chiral oxazaborolidine catalyst directly. The corresponding chiral secondary alcohols were obtained with excellent enantiomeric excesses (93–99% ee) and good to excellent yield (80–99%).     

Untersuchungen zur Umsetzung von [Lithium(trimethylsilyl)amido]-methyl-trimethylsilylamino-silan Me(Me3SiNLi)(Me3SiNH)SiH mit verschiedenen Elektrophilen

Investigations of the Reaction between the [Lithium(trimethylsilyl)amido]-methyl-trimethyl-silylamino-silane Me(Me₃SiNLi)(Me₃SiNH)SiH and different Electrophiles The lithium silylamide Me(Me₃SiNLi)(Me₃SiNH)SiH 1 reacts with chlorotrimethylsilan in the nonpolar solvent n-hexane to the N-substitution product Me[(Me₃Si)₂N](Me₃SiNH)SiH 2 and to the cyclodisilazane [Me(Me₃SiNH)Si—N(SiMe₃)]₂ 3 nearly in same amounts. The reaction of 1 with chlorotrimethylstannane gives besides small amounts of the cyclodisilazane 3 the N-substitution product Me[(Me₃Si)(Me₃Sn)N](Me₃SiNH)SiH 4 . By the reaction of 1 with trimethylsilyltriflate the cyclodisilazane 3 is obtained as the main product. Furthermore 2 and the cyclodisilazane 5 are formed. Ethylbromide shows no reaction with 1 under the same conditions. These results indicate the existence of an equilibrium of the lithium silylamide 1 , the silanimine Me(Me₃SiNH)Si?N(SiMe₃) and lithium hydride.     

CNN Pincer Ruthenium Catalysts for Hydrogenation and Transfer Hydrogenation of Ketones: Experimental and Computational Studies

Reaction of [RuCl(CNN)(dppb)] ( 1‐Cl ) (HCNN=2‐aminomethyl‐6‐(4‐methylphenyl)pyridine; dppb=Ph₂P(CH₂)₄PPh₂) with NaOCH₂CF₃ leads to the amine‐alkoxide [Ru(CNN)(OCH₂CF₃)(dppb)] ( 1‐OCH₂CF₃ ), whose neutron diffraction study reveals a short RuO ??? HN bond length. Treatment of 1‐Cl with NaOEt and EtOH affords the alkoxide [Ru(CNN)(OEt)(dppb)] ? (EtOH)_n ( 1‐OEt?n EtOH ), which equilibrates with the hydride [RuH(CNN)(dppb)] ( 1‐H ) and acetaldehyde. Compound 1‐OEt?n EtOH reacts reversibly with H₂ leading to 1‐H and EtOH through dihydrogen splitting. NMR spectroscopic studies on 1‐OEt?n EtOH and 1‐H reveal hydrogen bond interactions and exchange processes. The chloride 1‐Cl catalyzes the hydrogenation (5 atm of H₂) of ketones to alcohols (turnover frequency (TOF) up to 6.5×10⁴ h^?1, 40 °C). DFT calculations were performed on the reaction of [RuH(CNN′)(dmpb)] ( 2‐H ) (HCNN′=2‐aminomethyl‐6‐(phenyl)pyridine; dmpb=Me₂P(CH₂)₄PMe₂) with acetone and with one molecule of 2‐propanol, in alcohol, with the alkoxide complex being the most stable species. In the first step, the Ru‐hydride transfers one hydrogen atom to the carbon of the ketone, whereas the second hydrogen transfer from NH₂ is mediated by the alcohol and leads to the key “amide” intermediate. Regeneration of the hydride complex may occur by reaction with 2‐propanol or with H₂; both pathways have low barriers and are alcohol assisted.     

Reaktionen des tBu(Me3Si)P?P(Li)?P(tBu)2 mit CH3Cl und 1,2-Dibromethan

Reactions of tBu(Me₃Si)P? P(Li)? P(tBu)₂ with CH₃Cl and 1,2-Dibromoethane tBu(Me₃Si)P? P(Li)? P(tBu)₂ · 0.95 THF 1 with CH₃Cl (?70°C) yields tBu(Me₃Si)P? P = P(Me)(tBu)₂ 2 at ?70°C, with 1,2-Dibromoethane tBu(Me₃Si)P? PBr? P(tBu)₂ 3 (main product) and tBu(Me₃Si)P? P?P(Br)tBu₂ 4. 3 eliminates Me₃SiBr yielding the cyclotetraphosphane {tBuP? P[P(tBu)₂]}₂ 5 .     

Die 3-(N,N-Dimethylamino)prop-1-enyl-Gruppe als Chelatligand in Organoindium-Verbindungen

The 3-(N,N-Dimethylamino)prop-1-enyl Group as a Chelate Ligand in Indium Organyls InBr₃ reacts with Me₂NCH₂CH?CHMgCl (molar ratio 1 : 2) to form (Me₂NCH₂CH?CH)₂InBr ( 1 ) as the first indium alkenyl compound with amino-functionalized alkenyl groups. The X-ray structure determination shows the formation of a chelate complex. 1 crystallizes in the orthorhombic space group Fddd with the unit cell parameters a = 14.904(2) Å, b = 17.140(1) Å and c = 21.035(2) Å. By reaction of Me₂InBr with Me₂NCH₂CH?CHMgCl (molar ratio 1 : 1) (Me₂NCH₂CH?CH)InMe₂ ( 2 ) is formed as a colorless, at room temperature liquid, monomeric compound. The n.m.r. and mass spectra are discussed.     

Transition Metal Chemistry of Main Group Hydrazides. 17. Triphosphine derived from phosphanyl hydrazide as a building block for hetero trimetallic compounds. Synthesis and coordination chemistry of ((Me2P)2N?N(Me)(PMe2))

The new triphosphine (Me₂P)₂N? N(Me)(PMe₂) ( 1 ), has been synthesized in pure form by the reaction of methylhydrazine with dimethylchlorophosphine in the presence of triethylamine. This triphosphine represents a bridge between phosphinoamine (>P? N(R)? P<) and phosphanyl hydrazide (>P? N(R)? N(R)? P<) backbones. Reaction of 1 with cis-[W(CO)₄(NHC₅H₁₀)₂] proceeds via two coordination modes to give four-membered M? P? N? P and five-membered M? P? N? N? P metallacyclic frameworks. The tungsten complex cis-[W(CO)₄{(Me₂P)₂NN(Me)(PMe₂)}] ( 2 ) possessing an uncoordinated phosphine moiety to prepare multimetallic organometallic compounds. For example, reactions of 2 with PdCl₂(PhCN)₂ and PtCl₂(COD) produced the trimetallic complexes consisting of W(0)? Pt(II) and W(0)? Pd(II) centers respectively in good yields. The different isomers of these trinuclear complexes have been clearly identified by ³¹P NMR spectroscopy.     

Synthesis and magnetic properties of binuclear cobalt(Ⅱ), nickel(Ⅱ) and copper(Ⅱ) complexes bridged by oxamidate group

Four binuclear Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) complexes bridged by oxamidate (oxd) group have been synthesized, namely Co2(byp)2(oxd)(ClO4)2 (1), Co2(Me2bpy)2(oxd)(ClO4)2.H2O (2), Ni2(bpy)2(oxd)(ClO4)2.2H2O (3) and Cu2(Me2bpy)2(oxd)(NO3)2 (4). (bpy=2,2'-bipyridyl, Me2-bpy=4,4'-dimethylbipyridyl, oxd=oxamidate) The complexes are characterized by IR, UV spectra, EPR and variable-temperature magnetic susceptibility (4-300 K). The susceptibility data for. complexes 1 and 3 were least-squares fit to the susceptibility equation derived from the spin Hamiltonian H=-2J . S1 . S2. The exchange integral, J, was found to be equal to -3.62 cm-1 in 1 and -1.82 cm-1 in 3. This indicates a weak antiferromagnetic spin exchange interaction between the metal ions.     

Single Oxygen‐Atom Insertion into PB Bonds: On‐ and Off‐Metal Transformation of a Borylphosphine into a Borylphosphinite

An oxygen atom is selectively inserted into the P?B bond of a borylphosphine ( L₁ ) by reaction with Me₃NO to afford the corresponding borylphosphinite ( L₂ ). This transformation can also be effected when L₁ is coordinated to rhodium. The ν(CO) values for trans‐[RhCl(CO)(L)₂] reveal very different electronic properties for coordinated L₁ and L₂ which translate into the strikingly different performances of the complexes [RhCl(L)(cod)] (L= L₁ or L₂ , cod=1,5‐cyclooctadiene) in hydrosilylation and hydroboration catalysis.     

Alternativ-Liganden. XXII. Rhodium(I)-Komplexe mit Donor/Akzeptor-Liganden des Typs Me2PCH2CH2SiXnMe3−(X = F,Cl, OMe)

Alternative Ligands. XXII. Rhodium(I) complexes with Donor/Acceptor Ligands of the Typs Me₂PCH₂CH₂SiX_nMe_3?n(X = F, Cl, OMe) Donor/acceptor ligand of the type Me₂PCH₂SiX_nMe_3?n react with [Rh(CO)₂Cl]₂ ( 1 ) to give the mononuclear complexes RhCl(CO)(PMe₂CH₂CH₂SiX_nMe_3?n)₂ ( 2-6 , Table 1) with planar geometry of the donor atoms, one exception being Me₂PCH₂CH₂CH₂SiCl₃, yielding the crystalline Rh^III-complex RhCl₂(CO)(PMe₂CH₂CH₂SiCl₂)(PMe₂CH₂CH₂SiCl₃) ( 7 ) by oxidative addition of one of the SiCl bonds to the Rh¹ precursor. Structures with Rh → Si interaction between the basic central atoms and the acceptor group SiX_nMe_3?n could be detected in the isolated products neither spectroscopically nor by X-ray diffraction of the two representatives RhCl(CO)(PMe₂CH₂CH₂SiF₃)₂ ( 2 ) and RhCl(CO)[PMe₂CH₂CH₂siF₃]₂ ( 2 ) and RhCl(CO) [PMe₂CH₂CH₂Si(OMe₃]₂ ( 6 ). The presence of such acid/base adducts in the reaction mixture is indicated for the more acidic acceptor groups SiX_nMe_3?n byv_co values near 1990cm^?1, (see Table 3). The complex RhCl(CO)PMe₃)(PMe₂CH₂CH₂SiF₃ ( 8 ) is obtained by the reaction of RhCl(CO)(PMe₃)₂ ( 9 ) with Me₂PCH₂SiF₃ and has been identified spectroscopically in a mixture with 2 and 9 .     

Katalytische Carbonylierung von Aceton-oxim an Bisoximato-diruthenium-Komplexen: Ein einfacher Zugang zu wasserfreiem Acetonin. Isolierung und Molekülstruktur von [Ru2(CO)5(Me2CNO)2(Me2CNOH)]

Catalytic Carbonylation of Acetone Oxime at Bisoximatodiruthenium Complexes: A Simple Access to Anhydrous Acetonine. Isolation and Molecular Structure of [Ru₂(CO)₅(Me₂CNO)₂(Me₂CNOH)] In the presence of catalytic amounts of [Ru₂(CO)₄(Me₂CNO)₂(Me₂CNOH)₂] ( 1 ), acetone oxime reacts with carbon monoxide to give 2,3,4,5-tetrahydro-2,2,4,4,6-pentamethylpyrimidine (‘acetonine’). CO₂, and NH₃. The reaction proceeds presumably via carbonylation of Me₂C?NOH to the unstable intermediate Me₂C?N? OCHO which undergoes decarboxylation to give the corresponding imine Me₂C?NH. The final product is assumed to result from the cyclotrimerisation of Me₂C?NH with elimination of NH₃. Evidence for the intermediacy of the imine comes from the analogous reaction of acetophenone oxime, PhMeC?NOH, which gives the corresponding imine PhMeC?NH as a stable product. The isolation of the complex [Ru₂(CO)₅(Me₂CNO)₂(Me₂CNOH)] ( 2 ) suggests the carbonylation to take place at the bridging oximato ligand of 1 .     

Dehydrogenation of Amine?Borane Me2NH⋅BH3 Catalyzed by a Lanthanum?Hydride Complex

The rare‐earth‐metal? hydride complexes [{(1,7‐Me₂TACD)LnH}₄] (Ln=La 1 a , Y 1 b ; (1,7‐Me₂TACD)H₂=1,7‐dimethyl‐1,4,7,10‐tetraazacyclododecane, 1,7‐Me₂[12]aneN₄) were synthesized by hydrogenolysis of [{(1,7‐Me₂TACD)Ln(η³‐C₃H₅)}₂] with 1 bar H₂. The tetrameric structures were confirmed by ¹H NMR spectroscopy and single‐crystal X‐ray diffraction of compound 1 a . Both complexes catalyze the dehydrogenation of secondary amine? borane Me₂NH ? BH₃ to afford the cyclic dimer (Me₂NBH₂)₂ and (Me₂N)₂BH under mild conditions. Whilst the complete conversion of Me₂NH ? BH₃ was observed within 2 h with lanthanum? hydride 1 a , the yttrium homologue 1 b required 48 h to reach 95 % conversion. Further reactions of compound 1 a with Me₂NH ? BH₃ in various stoichiometric ratios gave a series of intermediate products, [{(1,7‐Me₂TACD)LaH}₄](Me₂NBH₂)₂ ( 2 a ), [(1,7‐Me₂TACDH)La(Me₂NBH₃)₂] ( 3 a ), [(1,7‐Me₂TACD)(Me₂NBH₂)La(Me₂NBH₃)] ( 4 a ), and [(1,7‐Me₂TACD)(Me₂NBH₂)₂La(Me₂NBH₃)] ( 5 a ). Complexes 2 a , 3 a , and 5 a were isolated and characterized by multinuclear NMR spectroscopy and single‐crystal X‐ray diffraction studies. These intermediates revealed the activation and coordination modes of “Me₂NH ? BH₃” fragments that were trapped within the coordination sphere of a rare‐earth‐metal center.