bluuebunny/crossref_metadata_2025_split huggingface dataset:
Diorganomagnesium Compounds from Magnesium, Hydrogen, and 1‐Alkenes and Their Application in Synthesis
Authors: Bogdanović Borislav , Bons Peter , Konstantinović Stanimir , Schwickardi Manfred , Westeppe Uwe 
Published: July 2007

Abstract1‐Alkenes are converted in high yields to the corresponding primary diorganomagnesium compounds by transition metalcatalyzed hydromagnesation reaction using catalytically prepared suspended (MgH2*) or dissolved magnesium hydride (MgH2*). The most active hydromagnesation catalysts have been found to be combinations of zirconium tetrahalides with MgH2* or MgH2*. The reaction is highly regio‐and chemoselective. The diorganomagnesium compounds prepared in situ from magnesium, hydrogen, and 1‐alkenes can be applied to the synthesis of organic and organometallic compounds just as Grignard compounds (Scheme 3, reaction 3–11). Dioctylmagnesium undergoes the growth reaction with ethene in the presence of quinuclidine and is oxidized by molecular oxygen in high yield to 1‐octanol.
Organosubstituierte 1,1′‐Spirobisilole und 1,1′‐Spirobigermole durch vierfache Organoborierung von Tetra‐1‐alkinylsilanen und ‐germanen
Authors: Köster Roland , Seidel Günter , Klopp Ingo , Krüger Carl , Kehr Gerald , Süß Jürgen , Wrackmeyer Bernd 
Published: July 2007

Organosubstituted 1,1′‐Spirobisiloles and 1,1′‐Spirobigermoles by Fourfold Organoboration of Tetra‐1‐alkynylsilanes and ‐germanes[1]Si(CCR)4 [RMe (A), RPh (B), RSiMe3 (C)] and Ge(CCR)4 [RMe (D), RPh (E)] react with Et3B by twofold intermolecular ethyloboration and twofold intramolecular vinyloboration to form the organo‐substituted 5‐sila(germa)spiro[4.4]nonatetraenes , RMe: 1a, RPh: 1b; MGe, RMe: 2d, RPh: 2e] via the mono‐and bisethyloboration compounds 3 or 4 (e.g. 3b, 4c) with different rates: Ge > Si; Me > Ph. For comparison, compounds Sn(CCR)4 [RMe (F), RPh (G)] react with Et3B in the absence of a solvent to mixtures of various spirotin compounds (5f, 5g, 6f, 8f, 9g, 10g, 11g) of which only 9g (RPh) corresponds to the spirosilanes and ‐germanes. This is the result of effective competition between intramolecular and intermolecular organoboration in the case of the tetra‐1‐alkynyltin compounds. The protodeborylation of 1a, b and 2d, e with MeCO2H leads to 12a, b and 13d, e, respectively. 12a isomerises by UV irradiation to allyl isomers 12a′. From 12a with 2 equiv. of maleic anhydride the 1:2 addition compound 14a is obtained, the autaddition of 12a, d leads to 15a, d. Spiro compound 12a reacts with (OC)5Fe or CpCo(C2H4)2 to give the cyclodiastereomeric η41‐complexes [(OC)3Fe]2‐12a (16a1–a4; X‐ray structure analysis of meso‐ 16a1), (OC)3Fe‐12a (17a) and (CpCo)2‐12a (18a1–a4). – All products were characterized by multinuclear NMR, including measurements of the coupling constants 1J(13C13C), 2J(29Si29Si), nJ(29Si13C) and nJ(119Sn13C).
2‐Boraindane und 2‐(Dialkylamino)1‐2‐benzoborol‐Dianionen
Authors: Herberich Gerhard E. , Eigendorf Uwe , Englert Ulli 
Published: July 2007

2‐Boraindanes and 2‐(Dialkylamino)1‐2‐benzoborole Dianionsortho1‐Xylene reacts with the Lochmann‐Schlosser base to produce a mixture of the potassium derivatives K2[1,2‐C6H4(CH2)2] (2) and K[2‐MeC6H4CH2] (3). Condensation of 1 + 2 with BCl2(NR2) (RMe, Et, iPr) affords 2‐(dialkylamino)1‐2‐boraindanes (1a–c) (50%). Treatment of 1a, b with LiTMP/TMEDA in THF yields dilithio derivatives [Li(tmeda)]2[C6H4(CH)2BNR2] (8a, b) (40%) which show tripledecked structures consisting of an aromatic 10′‐electron 2‐benzoborole dianion and two [Li‐(tmeda)]+ units facially bound to the borole ring. 1a reacts with HCl/Et2O/hexane to give C6H4(CH2)2BCl · OEt2 (1d · OEt2) (76%) which decomposes in vacuo to give the chloro derivative 1d. The methyl derivative C6H4(CH2)2BMe (1e) is obtained from 1a by treatment with LiMe/Et2O at –78°C and subsequently with HCl/Et2O at –78°C (41%). 1a, b react with MeOH at –78°C to give solid adducts C6H4(CH2)2BOMe · NHR2 (12a, b) while 1c affords C6H4(CH2)2BOMe (1f). Subsequent ring‐opening produces 2‐MeC6H4CH2B(OMe)2 (13). With the exception of 1b the 2‐boraindanes 1 are crystalline solids. The silylation of the 2‐benzoborole dianions and various (2‐methylbenzyl)borane derivatives is also described.
From para1‐Dimethoxybenzene Toward Crownbenzenophanes, 2. Synthesis, X‐ray Structure and Fluorescence Emission Properties of 1,3,10,13,16,19,22‐Heptaoxa(3,13)[28]paracyclophane and Its Complex with Sodium Cation
Authors: Marsau Pierre , Andrianatoandro Harimbola , Willms Thomas , Desvergne Jean‐Pierre , Bouas‐Laurent Henri , Hopf Henning , Utermöhlen Ralf 
Published: July 2007

AbstractThe synthesis and X‐ray molecular structure of the title compound, an heptaoxa[3,13]paracyclophane, as well as that of its 1:1 sodium complex are described; a study of the absorption and fluorescence spectra indicates that this crown‐cyclophane behaves as a hybrid between strained classical cyclophanes and large macrocycles.
Synthese von Tetravinylphthalocyanin
Authors: Beck Anton , Hanack Michael 
Published: July 2007

Synthesis of TetravinylphthalocyanineTetravinylphthalocyanine (5) has been prepared by heating 1,3‐dihydro‐1,3‐diimino‐5‐vinyl‐isoinodole (4) in DMAE. 5 is characterized by IR‐, UV/Vis‐, and 13C CP/MAS‐NMR spectroscopy.
Diels‐Alder Reaction of Racemic β1‐Isopropyl‐α1‐methylene‐β1‐lactone with Enantiomerically Pure 5,6,7,7a‐Tetrahydro‐7a‐methyl‐1‐phenyl‐4H1‐indene and Retro Cleavage of the Resulting Spiro‐β1‐lactones: The First Case of a Perfect Topological Resolution
Authors: Adam Waldemar , Nava Salgado Victor O. , Wegener Bernd , Winterfeldt Ekkehard 
Published: July 2007

AbstractThe racemic β1‐isopropyl‐α1‐methylene‐β1‐lactone 1 undergoes a configuration‐dependent, highly selective [4 + 2] cycloaddition to the enantiomerically pure cyclopentadiene 2; chromatographic separation of the adducts and subsequent thermal retro cleavage provide the pure enantiomers (S)‐1 and (R)‐1 in 99% e.e.
Darstellung und Reaktionen von (η3‐Allyl)(η5‐pentamethylcyclopentadienyl)‐cobalt(II) und seinen Derivaten
Authors: Nehl Hans 
Published: July 2007

Synthesis and Reactivity of (η3‐Allyl)(η5‐pentamethylcyclopentadienyl)cobalt(II) and its DerivativesReaction of (η5‐pentamethylcyclopentadienyl)cobalt(II) chloride (1) with allyllithium‐ or allylmagnesium compounds leads to new (η3‐allyl)(η5‐pentamethylcyclopentadienyl)cobalt(II) complexes 2a–d. Complexes 2a reacts with acetonitrile by oxidative addition of a methyl group to cobalt to form 5. With alkynes complexes with cyclodimerisized or ‐trimerisized alkynes as ligands are formed, e.g. the tetraphenylcyclobutadiene complex 6 from 2a and tolan and the hexamethylbenzene complex 8 from 2a and 2‐butyne. Reaction with phenylethyne catalytically leads to triphenylbenzene 10. The complexes 2a–d are oxidized by iodine and bromine to Co(III) iodides 12a–d and bromides 14a and b and by ferricenium tetrafluoroborate to the tetrafluoroborates 13–c. The tetrafluoroborates give with nitriles stable complexes (nitrile‐co‐ordinated end‐on to Co), with alkynes substituted cyclopentadienyl ligands coordinated to Co are formed by cycloaddition of the allyl group and the alkyne.
Lanthanoiden‐Komplexe, V[1]. Strukturchemie ein‐ und zweikerniger Seltenerdalkoxide
Authors: Herrmann Wolfgang A. , Anwander Reiner , Scherer Wolfgang 
Published: July 2007

Complexes of the Lanthanides, V[1].–Structural Chemistry of Monomeric and Dimeric Rare Earth AlkoxidesThe first sublimable monomeric yttrium „CH‐alkoxide”︁ Y[OC‐(iPr)(tBu)2]3 (3) is obtained by the reaction of „CH‐alcohol”︁ HOCiPr(tBu)2 („H‐proditox”︁, 1) with Y[N(SiMe3)2]3 (2). The importance of metal‐ion size and ligand sphere for nucleation is demonstrated for the system „Ln/ditox/acetonitrile”︁. The crystal structure data of dimeric 4 (Ln=Nd) and monomeric 5 (Ln=Dy) once again support the ionic nature of lanthanide alkoxide complexes.
Synthesis, X‐ray and Electronic Structure of Trinickel Tetradecker Sandwich Complexes {(η5‐C5H5)Ni[μ,η5‐(CR1)2(BR2)2CR3]}2Ni
Authors: Siebert Walter , Herter Wilfried , Schulz Hartmut , Huck Stefan , Pritzkow Hans , Zhu Longgen , Eisenstein Odile 
Published: July 2007

AbstractThe reduction of the 18‐VE complexes (η5C5H5)Ni[η5‐(CR1)2(BR2)2CR3] (2a, b) with potassium in THF leads to the paramagnetic anions 2–, which react with NiBr2 · DME to give the triple‐decker complexes (η5‐C5H5)Ni[μ,η5‐(CR1)2(BR2)2CR3]Ni(η5‐C5H5) (3a, b) and the tetradecker {(η5‐C5H5)Ni[μ,η5‐(CR1)2(BR2)2CR3]}2Ni (4b). Surprisingly, 4b is also obtained by heating the double‐decker complex 2b and H2AlOCMe3 in THF. The reaction between 2c and AlH3 in Et2O leads to the substitution of the ethoxy groups at the boron atoms and to the formation of the tetradecker 4d with four B–H groups. Heating of the 1,3‐benzodiborole ligand 1e and [(C5H5)Ni(CO)]2 in toluene yields small amounts of 2e and 3e, and the tetradecker 4e. X‐ray structure analyses were performed for 4d and 4e. Complex 4d is centrosymmetric with relatively short nickel‐to‐bridging ligand distances (1.69, 1.70 Å). In the tetradecker 4e the two bridging ligands adopt a synclinal conformation (rotating about 36° resp. 41° against each other). The Ni–Ni distance (3.42, 3.43) is slightly longer than in 4d (3.39 Å). The electronic structures of the tripledecker cation 3+ (32 VE) and of the tetradecker 4 (46 VE) have been investigated by means of the Fenske‐Hall method. The findings are in agreement with the experimental results that 3+ is a triplet species and 4 possesses a closed‐shell electron configuration.
Preparation and Properties of New Methano‐Bridged Dibenzo[c,g]phenanthrenes
Authors: Puls Carsten , Stolle Andreas , Meijere Armin De 
Published: July 2007

AbstractIntramolecular Friedel‐Crafts alkylation of 1‐(hydroxymethyl)[5]helicenes 1‐R and 15‐Me leads to 10,11‐methano‐bridged dibenzo[c,g]phenanthrenes 2‐R and 16‐Me, respectively. These molecules are shaped like the back of a turtle as shown by X‐ray crystal structure analysis. Their nonplanarity, however, is not rigid, as revealed by the temperature dependence of their 1H‐NMR spectra. With inversion barriers of about 62.4 and 67.1 kJ mol–1 2‐H and 2‐Me are surprisingly flexible. A remarkable diastereoselectivity is observed in the addition of methyl‐ and phenylmagnesium bromide to 1‐formyl[5]helicenes 14‐Me leading to secondary alcohols 15a, b‐Me, which cyclize to bridged hydrocarbons 16a, b‐Me, in which the substituents R=Me, Ph are in the thermodynamically less favorable endo‐position. Upon heating, endo‐16a,b‐Me isomerize to exo‐6a, b‐Me irreversibly.
Substituenteneffekte auf die C–C‐Bindungsstärke, 12[1]. Thermolysen aromatischer Pinakol‐dimethylether zur Bestimmung der Stabilisierungsenergie von α‐Methoxybenzyl‐Radikalen[2]
Authors: Birkhofer Hermann , Beckhaus Hans‐Dieter , Peters Karl , Schnering Hans‐Georg Von , Rüchardt Christoph 
Published: July 2007

Substituent Effects on the C–C Bond Strength, 12[1].–Thermolysis of Aromatic Pinacol Dimethyl Ethers and Stabilisation Energies of α‐Methoxybenzyl Radicals[2]The phenyl‐substituted pinacol dimethyl ethers meso‐ and DL‐ 5a–d have been prepared by reductive dimerisation of the dimethyl acetals 7a–d of the ketones 8a–d. 1H‐NMR spectra and GC‐retention times are used to distinguish between the diastereomers, and an X‐ray structure analysis of meso‐5a confirms these distinctive criteria. The products and the kinetics of the thermolysis reaction of 5a–d have been studied. A linear correlation between ΔG+ (300°C) of thermolysis and strain enthalpies Hs of 5, or its release Ds during the dissoziation into radicals 6, is observed. These correlations do not differ from those of the thermolysis of tetraalkyl‐diphenylethanes (1, R=alkyl, S=phenyl)[3,20a]. Hence, the methoxy group does not influence the homolysis reaction of the C–C bond in 5compared to an alkyl group. It is concluded that any stabilisation of the radicals 6 by the alkoxy group[1] is canceled by an extra stabilisation of 5 by the geminal phenyl/methoxy pairs.
Synthese mittlerer und großer Ringe, XXXIII[1]. Optisch aktive 3a,6‐Methanohydroazulene durch chirale Induktion der photochemischen Festkörperumlagerung von Bis(1,2:5,6‐di‐O‐isopropyliden‐α‐D‐ und ‐α‐L‐glucofuranos‐3‐O‐yl)‐3,6‐hexanooxepin‐4,5‐dicarboxylat
Authors: Tochtermann Werner , Schlösser Ulrike , Ott Frank , Popp Brigitta , Sdunnus Norbert , Snatzke Günther , Peters Eva‐Maria , Peters Karl , Schnering Hans Georg Von 
Published: July 2007

Synthesis of Medium and Large Rings, XXXIII[1].–Optically Active 3a,6‐Methanohydroazulenes via Chiral Induction of the Solid‐State Photochemical Rearrangement of Bis(1,2:5,6‐di‐O‐isopropylidene‐α‐D‐ and ‐α‐L‐glucofuranos‐3‐O‐yl) 3,6‐Hexanooxepine‐4,5‐dicarboxylateIrradiation of an aqueous suspension of the crystalline 3,6‐hexanooxepine‐4,5‐dicarboxylic esters 2a and 2b affords the (3aS,6R,8aR)‐ and (3aR,6S,8aS)‐methanohydroazulenes 3a and 4b in 54–58% yield with 92–93% de. Irradiation of an ethereal solution of 2a–2d on the other hand proceeds with low diastereoselectivity. The absolute configurations were established by X‐ray structural analysis of the dimenthyl ester (+)‐3d, comparison of CD spectra and chemical transformations. The origin of the high diastereoselectivity of the rearrangements 2a → 3a and 2b → 4b in the solid state is discussed on the basis of the X‐ray structural analysis of the 3,6‐heptanooxepine (–)‐5a. Procedures for the removal of the chiral auxiliaries are described. Di‐O‐isopropylidene‐α‐L‐glucofuranose is recycled in 95% yield.
Multibridged [3n]Cyclophanes, 1. Synthesis of [34](1,2,3,5)‐ and ‐(1,2,4,5)Cyclophanes
Authors: Shinmyozu Teruo , Kusumoto Shirou , Nomura Sachiyo , Kawase Haruo , Inazu Takahiko 
Published: July 2007

AbstractThe acid‐catalyzed cyclization of a pseudogeminally substituted acetyl group and a chloromethyl group of tri‐bridged cyclophane 7, followed by reduction of the carbonyl group afforded [34](1,2,3,5)cyclophane 3. One‐step TosMIC coupling reaction of tetrabromide 12 and subsequent reduction of the carbonyl groups provided an isomer of 3, [34](1,2,4,5)cyclophane 4.
Synthesis of 4‐Aminopyrimidines from 1,2,4‐Oxadiazoles, V[1]. Reductive Formation of 2‐(Benzoylamino)indole from 3‐(2‐Aminobenzyl)‐5‐phenyl‐1,2,4‐oxadiazole and Its Transformation to 6‐Phenyl‐8H‐pyrimido‐[1,6‐a: 4,5‐b']diindole, a New Heterocyclic Ring System
Authors: Bata Imre , Korbonits Dezső , Kolonits Pál , Podányi Benjamin , Takácsy‐Erős Tünde , Simon Kálmáan 
Published: July 2007

AbstractCatalytic hydrogenation of 5‐substituted 3‐(2‐aminobenzyl)‐1,2,4‐oxadiazoles 7 give 2‐(acylamino)indoles 10. Treatment of 2‐(benzoylamino)indoles 10a–c with acid leads to the novel 6‐phenyl‐8H‐pyrimido[1,6‐a: 4,5‐b']diindoles 19a–c. A route for the new ring formation is proposed. Catalytic hydrogenation of 19a (Raney nickel, 70°C, atmospheric pressure) saturates the 6‐phenyl ring but leaves the pentacyclic ring system intact. The structure of 19a is confirmed by an X‐ray crystallographic analysis.
On the Reaction of Nitrilium and N‐Acylamidinium Salts with Oximes and Other Hetero Nucleophiles
Authors: Glocker Michael O. , Shrestha‐Davadi Prativa Bade , Küchler‐Krischun Jonna , Hofmann Josef , Fischer Helmut , Jochims Johannes C. 
Published: July 2007

AbstractNitrilium salts 2 add oximes 1 to form stable alkylideneaminooxy‐substituted iminium salts 4. Compounds 4 have been postulated by Meerwein as intermediates of the Beckmann rearrangement of oximes[1]. For (E)‐4c an X‐ray structural analysis is performed. Other intermediates of the Beckmann rearrangement are the N‐acylamidinium salts 5, which are produced by the reaction of nitrilium salts with amides. As models for the transformation of 5 into amides, the end products of the Beckmann rearrangement, reactions of N‐acylamidinium salts with nucleophiles, e.g. oximes, alcohols, water, amines, thiols, and benzophenone imine are studied.
Organische Synthesen mit Übergangsmetall‐Komplexen, 64[1]. 1,4‐Diaminonaphthaline über Ketenimin‐Komplexe aus (β‐Aminovinylcarben)chrom‐Komplexen und Isocyaniden
Authors: Aumann Rudolf 
Published: July 2007

Organic Syntheses via Transition Metal Complexes, 64[1]. – 1,4‐Diaminonaphthalines via Ketenimine Complexes from (β‐Aminovinylcarbene)chromium Complexes and IsocyanidesThe thermal reaction of (dienylcarbene)chromium complexes (= 1‐chroma‐1,3,5‐trienes) with isocyanides provides a mild and regiospecific access to aromatic amines. Thus, 1,4‐diamino‐2‐ethoxynaphthalines 6a–d [1‐NHc‐C6H11; 4‐NRR1 = NMe2 (a) (S)‐2‐hydroxymethylpyrrolidinyl (b) (1R,2S)‐2‐methylamino‐1‐phenyl‐1‐propanol (c), NtBuMe (d)] are obtained by the cyclization of (E)‐(β‐aminostyrylcarbene)chromium complexes (CO)5Cr=C(OEt)CHC(NRR1)C6H5 [(E)‐3a–d] with cyclohexyl isocyanide (4) at 90°C in 72–85%. The aminocarbene complexes (E)‐3a–d are accessible with high stereoselectivity [>95% (E) configuration] and chemical yields of 91–96% by the addition of secondary amines HNRR1 2a–d to the (1‐alkoxy‐3‐phenylpropynylidene)chromium complex (CO)5Cr=C(OEt)C≡CC6H5 (1). 3 and 4 give initially mono‐ and bis(isocyanide) complexes, e.g. (E)‐8a and (E)‐9a, and subsequently dienylketenimine complexes by the insertion of 4 into the MC bond of 3. Dienylketenimine complexes are key intermediates in the formation of 6.
[α‐(Dimethylamino)benzyllithium–Diethyl Ether]2, (S)‐α‐(Methylpivaloylamino)benzyllithium – (–)‐Sparteine, and [3‐Iodo‐2‐lithio‐1‐methylindole – 2 Tetrahydrofuran]2: Crystal Structure Investigations of α‐Lithiated Amines
Authors: Boche Gernot , Marsch Michael , Harbach Jürgen , Harms Klaus , Ledig Burkhard , Schubert Frank , Lohrenz John C. W. , Ahlbrecht Hubertus 
Published: July 2007

AbstractIn order to determine whether α‐metalated (lithiated) amines are carbenoids, as are α‐lithiated halides and ethers, we have determined the crystal structures of the title compounds. In [α‐(dimethylamino)benzyllithium–diethyl ether]2 ([9 · OEt2]2) lithium bridges the anionic carbon and the nitrogen atom which corresponds to the most stable calculated model structure of LiCH2NH2. The C–N bond is only slightly (≈ 3 pm) elongated (compared to the neutral species). If one of the N‐methyl groups in [9 7dot; OEt2]2 is replaced by a pivaloyl group as in (S)‐α‐(methylpivaloylamino)benzyllithium – (–)‐sparteine (10 dot; sparteine), a five‐membered ring chelate is formed with Li being bound to the benzylic carbon atom and the oxygen atom of the pivaloyl group. In agreement with model calculations avoidance of the bridged structure as in [9 · OEt2]2 is compensated energetically by the chelate. Again a very small C–N bond elongation (≈ 3 pm) is observed. In [3‐iodo‐2‐lithio‐1‐methylindole – 2 THF]2 ([12 · 2 THF]2) lithium again does not bridge to the indole nitrogen atom because it is a weak donor. The C–N bond length to the anionic C atom is slightly longer (2–3 pm) than in the non‐lithiated compound. Other α‐lithiated amines, which have been published, although not analyzed so far under this particular aspect, show also a marginal C–N bond lengthening. However, since α‐lithiated amines – in contrast to α‐lithiated halides and ethers – until now have not been reported in the literature to react with nucleophiles RLi, there is no need to include them into the group of the above mentioned carbenoids – at least not to date.
Organophosphorverbindungen, 71[1]. Phosphaalkine und Phosphaalkene als Abfangpartner für 1,2‐Dehydrobenzol und Phenylium‐2‐carboxylat[2]
Authors: Breit Bernhard , Regitz Manfred 
Published: July 2007

Organophosphorus Compounds, 71[1]. – Phosphaalkynes and Phosphaalkenes as Trapping Partners for 1,2‐Dehydrobenzene and Phenylium‐2‐carboxylate[2]The reaction of benzene‐1‐diazonium‐2‐carboxylate (6) and of diphenyliodonium‐2‐carboxylate (7) with the phosphaalkynes 4 under thermal conditions leads to the formation of the 1,2‐dihydro‐1,3‐diphosphetes 10. With the phosphaalkenes 12 the benzenediazoniumcarboxylate 6 reacts with loss of nitrogen to give the so far unknown arylphosphaalkenes 13, the methanolysis of which afford the acylarylphosphanes 14. 1,2‐Dehydrobenzene (1), generated by β‐elimination starting with 15 or 16, does not react with the phosphaalkyne 4a (→ 5, R = tBu) but can be trapped by an insertion reaction with the phosphaalkenes 12 with formation of 17.
Umlagerungsreaktionen von Metallodiphosphapropenen des Typs (η5‐C5Me5)(CO)2FeP(SiMe3) — P = C(R)(SiMe3) (R = SiMe3, Ph)
Authors: Weber Lothar , Kirchhoff Ralf , Boese Roland 
Published: July 2007

Rearrangements of the Metallodiphosphapropenes (η5‐C5Me5)(CO)2FeP(SiMe3 — P = C(R)(SiMe3) (R = SiMe3, Ph)Heating of a methylcyclohexane solution of (η5‐C5Me5)‐(CO)2FeP(SiMe3) — P = C(SiMe3)2 (1a) gives rise to the insertion of the P = C moiety into the CH bond of a ring methyl group with formation of the chelate complex η5‐ηC5Me4CH2P‐[CH(SiMe3)2]P(SiMe3)Fe(CO)2 (2) which is converted into the pentacarbonylchromium derivative [5‐C5Me4CH2P[CH‐(SiMe3)2]P(SiMe3)[Cr(CO)5]Fe(CO)2] (3). In contrast, a similar treatment of (5‐C5Me5)(CO)2FeP(SiMe3) — P = C(Ph)(SiMe3) (1 b) furnishes the diphosphirane (5‐C5Me5)(CO)2FeP — C(Ph)‐SiMe3) — P (SiMe3) (5). By chromatography of its (CO)5Cr adduct 6, the P — Si bond is hydrolyzed to give the (diphosphirane)‐chromium complex [(5‐C5Me5)(CO)2FeP‐C(Ph)(SiMe3)P(H)]‐Cr(CO)5 (8). The molecular structures of 3 and 8 are determined by single‐crystal X‐ray analysis.
Derivatchemie des Clusters Ru4(CO)12(μ4‐η2‐N2Et2)
Authors: Hansert Bernhard , Vahrenkamp Heinrich 
Published: July 2007

Derivative Chemistry of the Cluster Ru4(CO)12(μ4η2‐N2Et2)The title compound (1) can be converted into H2Ru4CO)11(μ4‐η2‐N2Et2) (2) in three ways: a) by direct hydrogenation, b) by a H—/H+ sequence, c) by reduction with Na/Hg (reversible with FeCp2+/CO) and subsequent protonation. The structure of 2 has been determined by an X‐ray analysis. 2 is a dibasic acid and shows ligand fluxionality as demonstrated by NMR. 2 adds phenylacetylene either by insertion into one Ru—H bond or by H2 replacement yielding HRu4(CO)10(μ4‐N2Et2)(μ‐CPhCH2) (3) or Ru4(CO11(μ4‐N2Et2)(μ4‐HCCPh) (4).
Preparative, spectroscopic, and structural studies on some new silylamines
Authors: Mitzel Nobert W. , Riede Jürgen , Schier Annette , Paul Martin , Schmidbaur Hubert 
Published: July 2007

AbstractThe synthesis and characterization of two complete series of benzyl(phenylsilyl)amines (PhH2Si)x(PhH2C)3 — xN, benzyl(p‐tolylsilyl)amines (p‐H3CC6H4H2Si)x(PhH2C)3 — xN, and of bis‐(p‐tolylsilyl)amine are described. The compounds have been prepared from the corresponding amines and chlorosilanes with triethylamine as the auxiliary base. Bis(phenylsilyl)(trimethylsilyl)amine, (PhH2Si)2NSiMe3 (10), was obtained by the reaction of lithium bis(phenylsilyl)amide with chlorotrimethylsilane. Crystal structure analyses reveal that dibenzyl(p‐tolylsilyl)amine (7) and 10 contain planar nitrogen atoms. Heteronuclear NMR spectra (1H, 13C, 15N, and 29Si) have been measured for all compounds. The 15N chemical shifts are shown to be sensitive to variations of the geometry at the nitrogen atom. The coupling constants 1J(15N29Si) show a linear correlation with the N—Si bond lengths.