Tin(II) aminoalkoxides and heterobimetallic derivatives: the structures of Sn6(O)4(dmae)4, Sn6(O)4(OEt)4 and [Sn(dmae)2Cd(acac)2]2

Tin(II) methoxide reacts with N,N′‐dimethylaminoethanol (dmaeH) to yield Sn(dmae)₂ ( 1 ) along with small amounts of the hydrolysis product Sn₆(O)₄(dmae)₄ ( 2 ). The geometrically more regular iso‐structural cage Sn₆(O)₄(OEt)₄ ( 3 ) was obtained as the only tractable product isolated from reaction of 2 and Sb(OEt)₃, while 1 reacted with CdX₂ (X = acac, I) to afford Sn(dmae)₂Cd(acac)₂ ( 4 ) and Sn(dmae)₂CdI₂ ( 5 ). The X‐ray structures of 2, 3 and 4 are reported. Decomposition of 4 under aerosol‐assisted chemical vapour deposition conditions leads to amorphous tin oxide films with no detectable cadmium (i.e. ca < 2% cadmium), rather than a stoichiometric Sn:Cd oxide. Copyright © 2006 John Wiley & Sons, Ltd.     

Schwingungsspektren von Alkoxostibanen

Vibrational Spectra of Alkoxostibanes The vibrational spectra of the ethoxostibanes Sb(OEt)₃ ( 1 ), Sb(OEt)₂Cl ( 2 ), SbOEtCl₂ ( 3 ), Sb(OEt)₂Br ( 4 ), SbOEtBr₂ ( 5 ), and Sb(OEt)₂I ( 6 ) were assigned with the aid of the known structures of 2 and 3 in the solid state. The structures of 5 and 6 , which were prepared by new methods, differ from those of the corresponding chloro compounds. The coordination number of antimony in 5 and 6 is probable 5 and 4 resp.     

Oxide promoted isomerisation of an isonitrile complex,H2Os3(CO)10[CN(CH2)3Si(OEt)3]

The isomerisation of H₂Os₃(CO)₁₀[CN(CH₂)₃Si(OEt)₃] to HOs₃(CO)₁₀-[CN(H)(CH₂)₃Si(OEt)₃] is accelerated by interaction with some oxides; both complexes afford HOs₃(CO)₁₀[CN(H)(CH₂)₃Si(OEt)_3it-x(O)x] as oxide supported clusters.     

Insertion Reaction of Aldehydes into Zirconacyclopentanes

Aldehydes reacted with zirconacyclopentane derivatives via insertion into the Zr‐sp³C bond to afford the corresponding 7‐membered zirconacycles.     

Reactions of a Four-Membered Borete with Carbon,Silicon, and Gallium Donor Ligands: Fused and Spiro-Type Boracycles

Donor-acceptor cyclopropanes or cyclobutanes are dipolar reagents, which are widely used in the synthesis of complex organic (hetero)cycles in ring expansion reactions. Applying this concept to boron containing heterocycles, the four-membered borete cyclo-iPr₂N-BC₁₀H₆ reacted with the carbon donor ligands 2,6-xylylisonitrile and the carbene IMes :C(NMesCH)₂ with ring expansion and ring fusion, respectively. In particular, the tetracyclic structure formed with IMes displays zwitterionic character and absorption in the visible region. In contrast to the carbene IMes, the heavier carbenoids :Si(NDippCH)₂ and :Ga(AmIm) with a two-coordinate donor atom afford spiro-type bicyclic compounds, which display four-coordinate geometry at silicon or gallium. (TD-)DFT calculations provide deeper insight into the mechanism of formation and the absorption properties of these new compounds.     

Organometallic chemistry at the edge of polycyclic aromatic hydrocarbons

Zirconocene and bisphosphine nickel chemistry developed in our labs and directed towards the derivatization and synthesis of polycyclic aromatic carbon compounds is reviewed. Complexes with the formula Cp₂ZrMe(η¹-PAC) (PAC=anionic polycyclic aromatic carbon ligand) eliminate methane to produce zirconacycles and yne complexes. Treatment of the zirconacycles with L₂NiX₂ (L=phosphine, X=Cl, Br) in the presence of alkynes results in metallacycle transfer to nickel and cycloaddition of the alkyne. The resulting polycyclic aromatic carbon compounds contain an additional ring. The nickelacycles may also be accessed by oxidative addition of Ni(0) to polycyclic aromatic dihalides followed by reduction. The application of this chemistry to the step-growth synthesis of single-walled carbon nanotubes is proposed.     

1,1,3,3,3-Pentafluoro-2-pentafluorophenylpropene oxide. Precursor for novel phosphonates and ylides

1,1,3,3,3-Pentafluoro-2-pentafluorophenylpropene oxide reacted with triethyl phosphite to give the ylide C₆F₅(CF₃)C=P(OEt)₃. Hydrolysis yielded the phosphonate C₆F₅(CF₃)CHP(O)(OEt)₂, which was dehydrofluorinated using Et₃N · BF₃ to form the vinyl phosphonate C₆F₅(CF₂=)CP(O)(OEt)₂, a compound available also directly from the starting epoxide and diethyl trimethylsilyl phosphite. The vinyl phosphonate and diethyl trimethylsilyl phosphite furnished a 2:1 mixture of (Z) and (E) bisphosphonates together with fluorotrimethylsilane. Thermolylsis of the ylide gave diethyl phosphorofluoridate and 1,1-difluoro-2-pentafluorophenyl-but-1-ene. © 1997 John Wiley & Sons, Inc.     

Structures, stabilities, and equilibrium contents of C2-fragmentated C70 clusters

Density functional theory (DFT) calculations show that the C₂-fragmentation of C₇₀ destroys 4 of 37 original rings and generates 3 new rings, leading to 8 possible isomers. Each of those isomers contains a larger ring (7- or 8-member ring) with or without 4-member ring(s) besides 5- and 6-member rings. The most stable isomer consists of thirteen 5-member, twenty-two 6-member, and a 7-member rings without 4- and 8-member rings. The C₂-fragmentation energies (10.7–13.3 eV) of C₇₀ depend on resulted isomer-structures. Furthermore, the equilibrium fraction of the most stable isomer in the total isomers is 99.1%, 94.8%, and 94.0% at temperatures of 900, 1400, and 2000 K, respectively.     

Efficient and Selective Formation of Unsaturated Carboxylic and Phenylacetic Acids from Diketene

A nickel catalyst promotes the multicomponent coupling reaction of diketene, an alkyne, and Me₂Zn to provide 3‐methylene‐4‐hexenoic acids in excellent yields. Under similar conditions, the combination of the nickel catalyst and Et₂Al(OEt) promotes a cycloaddition reaction involving dimerization of an alkyne to furnish phenylacetic acids. In the presence of PPh₃, a formal [2+2+1+1] cycloaddition reaction proceeds to afford regioisomeric phenylacetic acids via cleavage of the C?C bond.     

Reaction of the Pincer‐type Ligand {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}— with [Ph3C]+[PF6]—. Unprecedented Rearrangement and Carbon‐Carbon Bond Formation

The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu‐C₆H₂}Li ( 1 ‐Li) with [Ph₃C]⁺[PF₆]^— gave the substituted biphenyl derivative 4‐[(C₆H₅)₂CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)₂]₂‐1, 1′‐biphenyl ( 5 ) which was characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu]C₆H₂}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)₂]₂C₆H₃ ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.     

Synthesis and structure of diamine bis(phenolate) complexes containing the Ti(OEt)–O–Ti(OEt) function

Reaction of diamine-bis(phenol) ligands containing a mixture of N-methyl and N,N′-dimethyl-N,N-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine, H₂L¹ and H₂L³, with [Ti(OCHMe₂)₄ in absolute ethanol under reflux without exclusion of air and moisture gives [(L¹)Ti (OEt–O–Ti(OEt)(L¹)] (1). [(L³)Ti(OEt)–O–Ti(OEt)(L³)] (2) forms when the remaining solution containing [(L³)Ti(OEt)₂] (3) (characterised by X-ray crystallography) is hydrolysed with H₂O. For the N-methyl and N,N′-dimethyl ligand mixture H₂L² and H₂L⁴, which contain tert-butyl groups on the ortho-positions of the aryl rings, [(L²)Ti(OEt)–O–Ti(OEt)(L²)] (4) forms much more slowly and [(L⁴)Ti(OEt)₂] (5) does not hydrolyse when H₂O is added. When the N-protonated ligand N,N-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁵, is used, rapid hydrolysis to two isomers of [(L⁵)Ti(OEt–O–Ti(OEt)(L⁵)] (6) occurs without addition of water. For N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)ethylenediamine, H₂L⁶, hydrolysis to [(L⁶)Ti(OEt)–O–Ti(OEt)(L⁶)] (7) occurs slowly when H₂O is added. For pendant NMe₂ ligand N,N-dimethyl-N′,N′-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁷, the hydrolysis reaction readily gives [(L⁷)Ti(OEt)–O–Ti(OEt)(L⁷)] (8) for which an X-ray crystal structure was obtained. The ortho-tert-butyl ligand derivative H₂L⁸ formed a complex analysing as [(L⁸)Ti(OEt)–O–Ti(OEt)(L⁸)] (9) which could not be studied further due to insolubility. Pendant pyridine ligand N-(2-pyridylmethyl)-N,N-bis(2′-hydroxy-3′-methyl-5′-tert-butylbenzyl)amine, H₂L⁹, apparently forms isomers of [(L⁹)Ti(OEt)–O–Ti(OEt)(L⁹)] and possibly [{(L⁹)Ti(O)}₂] from [(L⁹)Ti(OEt)₂] (10). The ortho-tert-butyl ligand derivative H₂L¹⁰ formed [(L¹⁰)Ti(OEt)–O–Ti(OEt)(L¹⁰)] (11) for which an X-ray crystal structure was obtained.     

Alkenylation of thiophenes and furans at the 2-position and a synthesis of allenes conjugated with α,β-unsaturated ester with magnesium alkylidene carbenoids

The reaction of 1-chlorovinyl p-tolyl sulfoxides, derived from ketones and chloromethyl p-tolyl sulfoxide, with i-PrMgCl at −78 °C gave magnesium alkylidene carbenoids. Treatment of the magnesium carbenoids with 2-lithiothiophenes and 2-lithiofurans resulted in the formation of 2-alkenylated thiophenes and furans, respectively, in good to high yields. The intermediates of these reactions were found to be alkenylmagnesium, which could be trapped with several electrophiles to afford thiophenes and furans bearing a fully substituted alkene at the 2-position. Treatment of the magnesium alkylidene carbenoids with 2-lithio-5-methoxyfuran afforded allenes conjugated with α,β-unsaturated methyl ester in moderate yields. These procedures offer a new and versatile one-pot synthesis of 2-alkenylthiophenes, 2-alkenylfurans, and allenes conjugated with α,β-unsaturated methyl ester from 1-chlorovinyl p-tolyl sulfoxides.     

Silicon and phosphorus alkoxide mixture: Sol-gel study by spectroscopic technics

Sol-gel synthesis of mixtures of tetraethoxysilane and a phosphorus alkoxide [P(OEt)₃ or (OEt)₂P-O-P(OEt)₂ or PO(OEt)₃] have been studied by ¹H, ¹³C²⁹Si and ³¹P liquid and solid state NMR, infrared and raman spectroscopies. This study shows different behaviors towards hydrolysis for these three different phosphates and phosphites. P(OEt)₃ almost instantly reacts with water to form an intermediate species HPO(OEt)₂, which slowly evolves first to HPO(OH)(OEt), then to HPO(OH)₂ a few days later. For (OEt)₂P-O-P(OEt)₂, the P-O-P bond is broken when water is added, then the same intermediates are formed faster. PO(OEt)₃ is hydrolyzed much slower than the other alkyl phosphates. After ten months, triethoxyphosphate is quantitatively present in the sol with little PO(OH)(OEt)₂ species. All these hydrolyzed species are well characterized. Only the system which contains the tetraethoxysilane and the triethoxyphosphite P(OEt)₃ forms a few P-O-P and P-O-Si bonds in the gel. Hydrolysis of tetraethoxysilane is much faster than that of phosphorus alkoxides and the conventional Q₂, Q₃ and Q₄ condensed silicon species form the gel three dimensional network.     

Electrochemical substitution of a carbonyl group by a phosphorus ligand in arenechromium tricarbonyl complexes

Electrochemical oxidation of (η-1,3,5-Me₃C₆H₃)Cr(CO)₃ in the presence of P(OEt)₃ with subsequent electrochemical reduction results in the formation of a (η-1,3,5-Me₃C₆H₃)Cr(CO)₂[P(OEt)₃] and (η-1,3,5-Me₃C₆H₃)Cr(CO)[P(OEt)₃]₂ mixture. Under similar conditions (η⁶-arene)Cr(CO)₃, where arene = 3,5-Me₂C₆H₃(CH₂)₂OPR₂ (R = OEt,OPh,F), yields the corresponding arenephosphite chelate complexes.     

The First [4+2]‐Coordinated Tetraorganolead Compound: Synthesis,Structure and Conversion into a Triorganolead Cation,a Benzoxaphosphaplumbole,and Diorganolead Dihalides

The syntheses and molecular structures, as determined by single‐crystal X‐ray diffraction analysis, of the first intramolecularly [4+2]‐coordinated tetraorganolead compound {4‐t‐Bu‐2, 6‐[P(O)(OEt)₂]₂C₆H₂}PbPh₃ ( 2 ) and the triphenyllead chloride adduct of the first intramolecularly coordinated benzoxaphosphaplumbole {[1(Pb), 3(P)‐Pb(Ph)₂OP(O)(OEt)‐5‐t‐Bu‐7‐P(O)(OEt)₂]C₆H₂·Ph₃PbCl} ( 3a ) are reported. The reaction of 2 with [Ph₃C]⁺ [PF₆]^— and p‐MeC₆H₄SO₃H, respectively, provides the triorganolead salts {4‐t‐Bu‐2, 6‐[P(O)(OEt)₂]₂C₆H₂}PbPh₂⁺X^— ( 4 , X = PF₆; 4a , X = p‐MeC₆H₄SO₃). Reaction of 2 with bromine and hydrogen chloride, respectively, gives the diorganolead dihalides {4‐t‐Bu‐2, 6‐[P(O)(OEt)₂]₂C₆H₂}PbPhX₂ ( 5 , X = Br; 6 , X = Cl).     

Enantioselective Denitrogenative Annulation of 1H‐Tetrazoles with Styrenes Catalyzed by Rhodium

Sulfonylation of 1H‐tetrazoles with triflic anhydride in the presence of chiral rhodium(II) carboxylate dimers causes denitrogenation to generate α‐azo rhodium(II) carbenoid species as new types of donor/acceptor carbenoids, which then readily react with styrenes to afford 3,5‐diaryl‐2‐pyrazolines with a high degree of enantioselectivity.     

Synthesis of conjugated enynes by assembly of three components, ketones, chloromethyl p-tolyl sulfoxide, and acetylenes, with the magnesium carbenoid 1,2-CC insertion as the key reaction

The reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from ketones and chloromethyl p-tolyl sulfoxide, with lithium acetylides gave adducts in moderate to good yields. Treatment of the adducts with Grignard reagents resulted in the formation of magnesium carbenoids by the sulfoxide-magnesium exchange reaction. 1,2-Carbon-carbon insertion (1,2-CC insertion) reaction of the generated magnesium carbenoids took place to afford conjugated enynes in good to high yields. This procedure provides a good method for the synthesis of multi-substituted conjugated enynes.     

Preparation of Hydride‐Ethylene Complexes of Osmium

Ethylene complexes [OsH(η²‐CH₂=CH₂)L₄]Y ( 1 , 2 ) [L = PPh(OEt)₂, P(OEt)₃; Y = OTf, BPh₄] were prepared by reacting the dihydride OsH₂L₄ first with methyl triflate CH₃OTf and then with ethylene (1 atm). Alternatively, the compound [OsH(η²‐CH₂=CH₂){PPh(OEt)₂}₄]OTf was prepared by allowing the dinitrogen derivative [OsH(N₂){PPh(OEt)₂}₄]OTf to react with ethylene. Acrylonitrile CH₂=C(H)CN reacts with OsH(OTf)L₄ [L = P(OEt)₃] to give the complex [OsH{κ¹‐NCC(H)=CH₂}{P(OEt)₃}₄]BPh₄ ( 3 ). The complexes were characterized spectroscopically (IR and ¹H, ¹³C, ³¹P NMR) and by X‐ray crystal structure determination of the [OsH(η²‐CH₂=CH₂){PPh(OEt)₂}₄]BPh₄ derivative.     

Direct Observation of the Binding Mode of the Phosphonate Anchor to Nanosized Polyoxotitanate Clusters

The structures of three newly synthesized phosphonate‐substituted polyoxotitanates are reported. The Ti/O core of [Ti₄O(OEt)₁₂(PhenylPO₃)] ( 1 ) is the building block for two larger phosphonate‐substituted nanoclusters, [Ti₂₅O₂₆(OEt)₃₆(PhenylPO₃)₆] ( 2 ) and [Ti₂₆O₂₆(OEt)₃₉(PhenylPO₃)₆]Br ( 3 ). All compounds exhibit a not previously recognized triply bridging binding mode of the phosphonate anchor with short connecting Ti? O bonds, the average of which is 2.010(7) Å. Comparison with previously reported work suggests that the binding mode of the phosphonate anchor is strongly dependent on the structure of the underlying substrate.     

Synthesis of Rhenabenzenes from the Reactions of Rhenacyclobutadienes with Ethoxyethyne

Treatment of Na[Re(CO)₅] with RC?CCO₂Et (R=phenyl, naphthalen‐1‐yl, phenanthren‐9‐yl and pyren‐1‐yl) followed by reaction with acetyl chloride and ethanol afforded the rhenacyclobutadienes Re{‐C(R)?C(CO₂Et)C(OEt)?}(CO)₄. Reactions of these rhenacyclobutadienes with HC?COEt produced rhenabenzenes Re{‐C(R)?C(CO₂Et)C(OEt)?CHC(OEt)?}(CO)₄. Except for R=Ph, new rhenacyclobutadienes with pendant alkenyl substituents Re{‐C(R)?C(C(OEt)?CH(CO₂Et))C(OEt)?}(CO)₄ were also isolated from these reactions. The NMR spectroscopic and X‐ray structural data, as well as the aromatic stabilization energy (ASE) values suggest that the rhenabenzenes are aromatic, with extensive delocalized π character.