bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and Molecular Structure of the Solvent‐Free [LiN(SiMe3)(2,6iPr2C6H3)]2 Dimer
Authors: Kennepohl Dietmar K. , Brooker Sally , Sheldrick George M. , Roesky Herbert W. 
Published: July 2007

Abstract[LiN(SiMe3)Ar]2 (1, Ar = 2,6‐iPr2C6H3) is prepared by the reaction of HN(SiMe3)Ar with nBuLi in n‐hexane. This compound with an unusual structure contains a four‐membered [LiN]2 heterocycle with two solvent‐free two‐coordinate Li centers. Its molecular structure represents the first solid‐state X‐ray analysis of an uncomplexed [LiN]2 dimer.
Kohlenwasserstoffverbrückte Komplexe XX Nucleophile Addition von Carbonylmetallaten an kationische Hexadienyl‐, Cycloheptadienyl‐, Cycloheptadienyl‐ und Cyclooctadienyl‐Komplexe von Eisen und Ruthenium: Heterodimetall‐Komplexe mit η1:η4‐C6‐, ‐C7‐ und ‐C8‐Kohlenwasserstoffbrücken
Authors: Niemer Burkhard , Breimair Josef , Wagner Barbara , Polborn Kurt , Beck Wolfgang 
Published: July 2007

Hydrocarbon‐Bridged Metal Complexes, XX. – Nucleophilic Addition of Carbonyl Metallates to Cationic Hexadienyl, Cyclohexadienyl, Cycloheptadienyl, and Cyclooctadienyl Complexes of Iron and Ruthium: Heterobimetallic Complexes with η1:η4, ‐C6, ‐C7, and ‐C8 Hydrocarbon BridgesThe addition of Re(CO)‐5, Mn(CO)‐5, and [(η5‐C5H5)W(CO)3]‐ to the cationic dienyl complexes [(η5‐dienyl)M(CO)3]+ (M = Fe, Ru; dienyl = hexadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, bicyclo[5.1.0]octadienyl) gives the heterobimetallic η1:η4‐hydrocarbon‐bridged complexes 1 – 4, 6, 7. In solution the initial nucleophilic adduct 2e of [(η5‐cyclo‐hexadienyl)Ru(CO)3]+ and [Re(CO)5]‐ rearranges to the complex 3, in which the Re(CO)5 group is bound to a sp2 carbon atom. By using Mn(CO)‐5 also the products of electron transfer between cation and anion have been observed. The crystal structures of (OC)3Fe(μ‐η4:η1‐hexadiene)Re(CO)5 (1), (OC)3Ru(μ‐η4:η1‐cyclohexadiene)Re(CO)5(3), (OC)3Fe(η4:η4‐C7H9—C7H9)Fe(CO)3 (5), (OC)3Ru(μ‐η4:η1‐cyclooctadiene)Re‐(CO)5 (6b), and of (OC)3Fe(η4:η1‐bicyclo[5.1.0]octadiene)‐Re(CO)5 (7) have been determined by X‐ray diffraction.
2,3‐Dioxo‐2,3‐dihydrofurane, 2 Vielseitige Synthese von 2,3‐Dioxo‐2,3‐dihydrofuranen und Alkylidenbutenoliden. – Kristall‐ und Molekülstruktur von 5‐(4‐Chlorphenyl)‐4‐methoxycarbonyl‐2,3‐dioxo‐2,3‐dihydrofuran
Authors: Saalfrank Rolf W. , Lutz Thomas , Hömer Bernd , Gündel Jürgen , Peters Karl , Schnering Hans Georg Von 
Published: July 2007

2,3‐Dioxo‐2,3‐dihydrofurans, 2. – Versatile Synthesis of 2,3‐Dioxo‐2,3‐dihydrofurans and Alkylidenebutenolides. – Crystal and Molecular Structure of 5‐(4‐Chlorophenyl)‐4‐methoxycarbonyl‐2,3‐dioxo‐2,3‐dihydrofuranReaction of the 1,3‐dicarbonyl compounds 5a – f, containing at least one α‐hydrogen atom in R1 and/or R2, with oxalyl halides 2 in the presence of magnesium chloride yields regioand on the whole stereospecifically the previously unknown (Z)‐alkylidenebutenolides 7a – f. Similarly, the 4‐alkoxycarbonyl‐5‐aryl‐2,3‐dioxo‐2,3‐dihydrofurans 6g – p are obtained (X‐ray structure of 61) starting from 3‐aryl‐3‐oxo‐propanoates 5g – p. Correspondingly, malondiamides 8a, b, e, f react with oxalyl chloride (2a) to give the 2,3‐dioxo‐2,3‐dihydrofurans 9a,b and 11a,b. Having mono(alkyl/aryl)amino substituents in position 5, compounds 11a,b spontaneously tautomerize to give imino enols 12a,b. Hydrochlorides 10a,b are formed on treatment of malondiamides 8c,d with oxalyl chloride (2a). In the case of the β‐oxocarboxamides 13/14 the substituents at the amide nitrogen atom control the regiochemistry. Starting from 13 (R2 = Ph) and oxalyl chloride (2a), 4‐acetyl‐5‐diphenylamino‐2,3‐dioxo‐2,3‐dihydrofuran (15) is formed regiospecifically, whereas under the same conditions 13/14 (R2 = CH2Ph) afford 4‐dibenzylcarbamoyl‐5‐methyl/phenyl‐2,3‐dioxo‐2,3‐dihydrofurans 16/17. Furanone 16 spontaneously enolizes to give 4‐dibenzylcarbamoyl‐3‐hydroxy‐5‐methylene‐2(5H]‐furanone (18). Similarly, the N‐monosubstituted β‐oxocarboxamides 19a,b readily react regiospecifically with oxalyl chloride (2a) to give via the 2,3‐dioxo‐2,3‐dihydrofurans 20a,b the imino enols 21a,b.
Organische Synthesen mit Übergangsmetall‐Komplexen, 54 Cyclopentadiene aus 1‐Metalla‐1,3‐dienen und Alkinen durch Cyclisierung intermediärer 1‐Metalla‐1,3,5‐triene (Metall = Wolfram)
Authors: Aumann Rudolf , Heinen Heinrich , Dartmann Mechthild , Krebs Bernt 
Published: July 2007

Organic Syntheses via Transition Metal Complexes, 54. — Cyclopentadienes from 1‐Metalla‐1,3‐dienes and Alkynes by Cyclization of Intermediate 1‐Metalla‐1,3,5‐trienes (Metal = Tungsten)We report on first examples of the formation of cyclopentadienes from a 1‐metalla‐1,3‐diene LnM=C‐C=C [LnM = W(CO)5] and an alkyne in [3 + 2] cycloaddition multistep reactions. In a first step the alkyne Et2N‐C=C‐Me (2) adds to the 1‐metalla‐1,3‐diene (CO)5W = C(OEt)‐CH=CHPh (1b) to give 1‐metalla‐1,3,5‐trienes (CO)5W=C(NEt2)‐CMe=C(OEt)‐CH=CHPh (3b) and (CO)5W=C(OEt)‐CH=C(NEt2)‐CMe=CHPh (4b). In a second step 3b cyclizes to thecyclopentadiene complex 5, which has an η1 ylide‐type structure as established by an X‐ray analysis. Hydrolysis of 5 leads to the formation of a 3‐aminocyclopentenone 7. The 1‐metalla‐1,3,5‐triene 4b yields a cyclopentadiene complex 8. In contrast to 5 the carbon skeleton of 8 has a connectivity different from that of the C3 unit of the 1‐metalla‐1,3‐diene 1.
Sulfur Compounds, 144 Synthesis of Sulfur‐Rich Organic Polysulfanes Utilizing Titanocene Pentasulfide as a Sulfur‐Transfer Reagent
Authors: Steudel Ralf , Förster Stefan , Albertsen Jörg 
Published: July 2007

AbstractTitanocene pentasulfide, Cp2TiS5 (1) reacts with Ph3CCl (4), C2H4(SCl)2 (6), and CH3C6H3(SCl)2 (9) to give the corresponding polysulfanes (Ph3C)5 (5), C2H4S7 (7), and CH3C6H3S7 (8) which have been characterized by NMR, mass, and Raman spectroscopy. By interconversion reactions the mentioned polysulfanes yield homologous molecules with up to 11 sulfur atoms which have been separated by reversed‐phase HPLC. Linear relationships between the capacity factor and the number of sulfur atoms in the molecule have been derived for each series, and retention indices have been calculated.
Epoxidation of Enol Silyl Ethers, Phosphates, Esters, and Lactones by Dimethyldioxirane
Authors: Adam Waldemar , Hadjiarapoglou Lazaros , Jäger Volker , Klicić Jasna , Seidel Bernhard , Wang Xiaoheng 
Published: July 2007

AbstractThe epoxides 2a–u (Table 1) of the enol silyl ethers 1a, b, enol phosphates 1c–k, and enol esters and lactones 11–u were prepared in excellent yields by epoxidation with isolated dimethyldioxirane (4) (as acetone solution). These labile epoxides (stable below 0°C) could be isolated in pure form and characterized spectroscopically (IR, 1H and 13C NMR). The derivatives 2p–u were sufficiently stable so that even C,H analyses were obtained. Warming up to room temperature led to rearrangement to the corresponding α‐oxy‐functionalized carbonyl products 3. Since epoxide 2c was sufficiently resistant towards hydrolysis, it could be prepared by the in situ method.
A Phosphine Complex of Bismuth(III): X‐ray Crystal Structure of [PMe3H][Bi2Br7(PMe3)2]
Authors: Clegg William , John Errington R. , Fisher George A. , Green Marjorie E. , Hockless David C. R. , Norman Nicholas C. 
Published: July 2007

AbstractThe reaction between BiBr3 and one equivalent of PMe3 in THF affords, after recrystallisation from MeCN/Et2O, yellow crystals of [PMe3H][Bi2Br7(PMe3)2]. 2 (MeCN) (1), which has been characterised by X‐ray crystallography. Compound 1 is the first reported bismuth‐phosphine complex and comprises a polymeric anion, the monomeric unit of which contains a planar Bi2Br6 core, each bismuth being further bonded to a PMe3 ligand and an additional bromide such that the bismuth resides in an octahedral coordination environment. The latter bromides form linear bridges between monomeric units; the phosphines are trans with respect to the Bi2 unit, with a Bi‐P distance of 2.762(3) A. The reaction between Bil3 and PEt3 in THF affords, after recrystallisation from MeCN/Et2O, orange crystals of [PEt4]4[Bi6I22] (3) which has also been characterised by X‐ray crystallography.
Cycloallene, 7 Ein Siebenringallen‐Dimer: Darstellung aus einem 7,7‐Dibromnorcaran‐Derivat und Thermolyse
Authors: Jelinek‐Fink Hans , Christl Manfred , Peters Eva‐Maria , Peters Karl , Schnering Hans Georg Von 
Published: July 2007

Cycloallenes, 7. – A Seven‐Membered‐Ring Allene Dimer: Preparation from a 7,7‐Dibromonorcarane Derivative and ThermolysisPrepared by addition of dibromocarbene to 1,2‐dihydro‐3‐phenylnaphthalene, the 7,7‐dibromonorcarane derivative 6 gave the tetra‐ and pentacyclic hydrocarbons 7 and 8, respectively, on treatment with n‐butyllithium. The formation of 8 is considered to proceed via the 1,2‐cycloheptadiene derivative 15, which undergoes a dimerisation with the tetramethyleneethane diradical 16 as intermediate. Diradical 16 is also believed to be the intermediate in the thermal rearrangements of 8 to the penta‐ and hexacyclic hydrocarbons 12 and 13 and of 12 to 13. The structures of 8 and 13 have been determined by X‐ray structure analyses. Of special interest is the unusual length (165 pm) of the C‐12a – C‐12b bond (C‐1 – C‐22 in Figure 1) in 8.
Synthese mittlerer und großer Ringe, XXX Regioselektive Thermolyse von Oligomethylen‐oxaquadricyclan‐dicarbonsäureestern zu 3,6‐Alkanooxepindicarbonsäureestern – Röntgenstrukturanalysen und semiempirische Rechnungen
Authors: Tochtermann Werner , Vogt Carola , Peters Eva‐Maria , Peters Karl , Schnering Hans Georg Von , Würthwein Ernst‐Ulrich 
Published: July 2007

Synthesis of Medium and Large Rings, XXX1). – Regioselective Thermolysis of Oligomethylene Oxaquadricyclanedicar‐boxylic Esters to 3,6‐Alkanooxepinedicarboxylic Esters – X‐ray Structural Analyses and Semiempirical CalculationsX‐ray structural analyses and semiempirical calculations for the oxaquadricyclanes 1 – 3 are discussed. The regioselectivity observed for the thermolyses of 1 – 3 (exclusive formation of 3,6‐alkanooxepines 6) is in line with the assumption that preferential cleavage of the long C – C bonds between the donor and acceptor substituents of the cyclopropane rings determines the reaction course.
Organoerdmetallkomplexe von d‐Block‐Elementen, III. Erste flüchtige Organogalliocobalt‐Verbindungen
Authors: Fischer Roland A. , Behm Joachim 
Published: July 2007

Organo Group‐13 Metal Complexes of d‐Block Elements, III. — First Volatile Organogallio Cobalt CompoundsIn non‐coordinating solvents, salt elimination between sodium tetracarbonylcobaltate and bulky alkylgallium chlorides yields almost quantitatively the novel volatile cobalt‐gallium complexes of formula (CO)4CoGaR2(L) [3a: R=CH2C(CH3)3; 3b: R=CH2Si(CH3)3; L=THF]. The synthesized compounds were identified by means of 1H‐, 13C‐, 31P‐NMR, MS, and infrared ν(CO) data. Additonal, 3a was characterized by an X‐ray single‐crystal analysis. The σ(Co–Ga) bond length is 257.8(3) pm. Those bonds are highly reactive and rapidly cleaved due to electrophilic or nucleophilic attack. 3a, b are used as canditates to generate intermetallic Co/Ga films by the procedure of low‐pressure MOCVD.
1λ5,3λ5‐Diphosphol‐Derivate aus Bis(diphenylphosphino)methan und Propargylbromiden
Authors: Schmidpeter Alfred , Stocker Johanna , Karaghiosoff Konstantin 
Published: July 2007

1λ5,3λ5‐Diphosphole Derivatives from Bis(diphenylphosphino)methane and Propargyl BromidesThe two title reagents 2 and 3 form a five‐membered 1,3‐diphosphole ring by nucleophilic interaction of the two phosphino groups of 2 with the methylene carbon atom and the adjacent acetylenic carbon atom of 3. (Phosphinomethyl)propargylphosphonium, diphosphafulvenium and diphospholium bromides (4, 6, and 1) result and can be isolated from consecutive steps of this reaction. By hydrolysis the diphospholium rings of 1 and 6 are selectively opened at the PCP unit to yield four different isomeric (phosphinoylpropenyl)phosphonium bromides 8—11.
Die Kristallstrukturen von {Li3(12‐Krone‐4)2[HC(CN)2]3}, {Na(15‐Krone‐5)‐[HC(CN)2]} und {Na[N(nBu)4][HC(CN)2]2 · THF}
Authors: Hiller Wolfgang , Frey Stephanie , Strähle Joachim , Boche Gernot , Zarges Wolfgang , Harms Klaus , Marsch Michael , Wollert RenéA , Dehnicke Kurt 
Published: July 2007

The Crystal Structures of {Li3(12‐crown‐4)2[HC(CN)2]3}, {Na(15‐crown‐5)[HC(CN)2]}, and {NaN(nBu)4[HC(CN)2]2 · THF}The preparation and the crystal structures of the title compounds 1—3 are described. 1 forms a polymeric chain structure, in which one of the lithium ions is linked by Li…NCC(H)CN… bridges. The remaining lithium ions form (12‐crown‐4)Li[NCC(H)CN] units, which are coordinated by one of the nitrogen atoms of the dicyanomethanide ions with the lithium ions of the chain. 2 forms an ion pair, in which the sodium ion is coordinated by the five oxygen atoms of the crown ether molecule and by one nitrogen atom of the dicyanomethanide ion. 3 has a threedimensional network, in which the sodium ions are coordinated in a distorted tetrahedral manner by the nitrogen atoms of the dicyanomethanide ions. In the cavities of the network the tetrabutylammonium ions and the THF molecules are found.
Mehrfachbindungen zwischen Hauptgruppenelementen und übergangsmetallen, CII. Flüchtige MN4‐Metallkomplexe von Niob und Tantal mit Dimethylsilyl‐Substituenten
Authors: Herrmann Wolfgang A. , Huber Norbert W. , Härter Peter , Denk Michael , Dyckhoff Florian 
Published: July 2007

Multiple Bonds between Main‐Group Elements and Transition Metals, CII[1]. — Volatile MN4 Metal Complexes of Niobium and Tantalum Containing Dimethylsilyl SubstituentsNiobium and tantalum complexes 4a and 4b of formula (Me2SiH)N=M[N(SiHMe2)2]3 (a: M=Nb; b: M=Ta) are formed from lithium bis(dimethylsilyl)amide and either MOCl3 (2a,b) or MCl5 (3a,b). No β‐hydrogen decomposition of these compounds occurs under normal conditions.
Alkylvanadium‐ und Alkylniobium‐Reagentien, II. Niobium‐induzierte reduktive Carbonyldimerisierung
Authors: Kauffmann Thomas , Kallweit Harry 
Published: July 2007

Alkylvanadium and Alkylniobium Reagents, II. — Niobium‐Induced Reductive Carbonyl DimerisationNbCl5 reacts with one equivalent of methyllithium or metallic potassium to give a reagent for the transformation of aldehydes, ketones, benzalchloride, and benzotrichloride to symmetrically substituted ethene derivatives (Tab. 1). The reagent NbCl5/K (2) is distinctly more reactive than NbCl5/MeLi (1). For the reductive carbonyl dimerisation with niobium reagents a mechanism is proposed.
Zum Mechanismus der Cyclopropan‐“Walk”‐Umlagerung: Synthese und Eigenschaften eines optisch aktiven Diazoalkan‐Addukts von Toluol; eine hochstereoselektive N2‐Eliminierung
Authors: Klärner Frank‐Gerrit , Band Rudiger , Glock Volker , König Wilfried A. 
Published: July 2007

Mechanism of the Cyclopropane “Walk” Rearrangement: Synthesis and Properties of an Optically Active Diazoalkane‐Toluene Adduct; a Highly Stereoselective N2 EliminationThe synthesis and the thermal and photochemical behavior of the optically active 2‐diazo‐1‐methoxypropane‐toluene adduct 3 are reported. The N2 elimination of 3 ocurs with one and the same stereochemical course upon thermolysis as well as direct photolysis: 7‐(Methoxymethyl)‐1,7‐dimethyl‐1,3,5‐cycloheptatriene (1) is formed with retention of configuration at C‐7 and 7‐(methoxymethyl)‐2,7‐dimethyl‐1,3,5‐cycloheptatriene (2) with inversion of configuration at C‐7. These stereochemical findings are explained by an intermediary singlet diradical 1[4] in which the ring closure between C‐1 and C‐7 or C‐5 and C‐7 is faster than the rotation around the single bond between C‐6 and C‐7. In the case of the thermally induced formation of 2 a concerted N2 elimination has to be considered as a competitive pathway. The results presented here are well in accord with the stereochemical analysis of the cyclopropane “walk” rearrangement 1⇋2 reported previously and are therefore a good evidence that the diradical intermediate 4 is also involved in the “walk” rearrangement. In the photochemically induced N2 elimination of 3, sensitized by benzophenone and leading again to 1 and 2, a surprisingly high degree of stereoselectivity is observed. Thus, the intermediary triplet diradical 3[4] must have a much shorter life time than ordinary 1,3‐diradicals in the triplet state.
2‐{[2‐(Dimethylamino)ethyl]methylamino}‐1,3,2‐benzodioxaphosphol als Ligand in Übergangsmetallkomplexen — Kristall‐ und Molekülstruktur eines Tetracarbonylchrom‐Komplexes
Authors: Kaukorat Thomas , Fischer Axel , Jones Peter G. , Schmutzler Reinhard 
Published: July 2007

2‐{[2‐(Dimethylamino)ethyl]methylamino}‐1,3,2‐benzodioxaphosphole as a Ligand in Transition‐Metal Complexes. Crystal and Molecular Structure of a Tetracarbonyl Chromium DerivativeComplexes of the zerovalent transition metals chromium, molybdenum, iron, and platinum react with the title phosphorus‐(III)‐compound 3 to give a range of different products: in the coordination compounds 4 and 5, 3 functions as a bidentate ligand, coordinating to the metal through the phosphorus and the nitrogen atom of the dimethylamino group. The structure of 4 was confirmed by a single‐crystal X‐ray analysis, showing a ligand “bite” angle of 91.0, 91.4° in two independent molecules. In the compounds 7 – 9, involving Mo, Fe, and Pt as a central atom, 3 coordinates solely through P(III). For the platinum(O) complex 9 31P‐NMR spectroscopy revealed a dynamic behaviour at room temperature.
Trichloro‐μ3‐[tris(diphenylphosphanyl)methane]‐trigold(I): Auriophilicity in a Triangle of Gold Atoms
Authors: Stützer Albert , Bissinger Peter , Schmidbaur Hubert 
Published: July 2007

AbstractTrichloro‐μ3‐[tris(diphenylphosphanyl)methane]‐trigold(I) (1) has been prepared by treating the tripod ligand tris(diphenylphosphanyl)methane with three equivalents of chloro(dimethyl sulfide)gold(I) in dichloromethane. 1 is converted into the tribromo (2), triiodo (3), and trimethyl derivatives (4) by treatment of suspensions of 1 in acetone with hydrogen bromide, potassium iodide, and methyllithium, respectively. Polycrystalline 1 has been studied by Mößbauer spectroscopy. From dichloromethane at room temperature cubic crystals of 1 are obtained, whereas at — 30° C a monoclinic dichloromethane solvate of 1 crystallizes. X‐Ray structure analyses have been performed for both forms. They contain essentially the same trinuclear complex with only marginal differences in the molecular dimensions. The striking structural feature of the complex is the triangular all‐cis arrangement of the three gold atoms with rather short Au…Au contacts of 3.201(1) (cubic) and 3.281(1)—3.420(1) Å (monoclinic). This conformation is at variance with the structures of the free ligand (all‐trans) and other adducts of the type HC(PPh2X)3 (cis/cis/trans) and is probably due to specific metal‐metal interactions.
Reaktive E = C(p—p)π‐Systeme, XXXI Erste Vertreter aminosubstituierter 1,2,4‐Diazaphosphole
Authors: Grobe Joseph , Van Due Le , Hegemann Marianne , Krebs Bernt , Läge Mechtild 
Published: July 2007

Reactive E = C(p—p)π Systems, XXXII[1]. — First Representatives of Amino‐Substituted 1,2,4‐Diazaphospholes(Diisopropylamino)phosphaethyne iPr2N—C≡P reacts at 20° C in a [3 + 2] cycloaddition with (trifluoromethyl)diazomethane (2a) or methyl diazoacetate (2b) to yield a mixture of the corresponding regioisomers 1H‐1,2,4‐diazaphospholes (5a or 5b) and 1H‐1,2,3‐diazaphospholes (6a or 6b) in quantitative yields (isomer ratio: 5a/6a = 2:1; 5b/6b = 4:1). X‐ray diffraction studies on 5a and 5b indicate a delicate charge balance in the bonding system of 1H‐1,2,4,σ2‐diazaphospholes under the influence of the exocyclic push/pull substituents iPr2N and CF3 or CO2Me, respectively.
Synthesis and Characterization of O‐Triorganosilyl Selenocarboxylates
Authors: Kato Shinzi , Kageyama Hideki , Kawahara Yasuyuki , Murai Toshiaki , Ishihara Hideharu 
Published: July 2007

AbstractA series of O‐triorganosilyl selenocarboxylates 2 are prepared by the reaction of sodium or potassium selenocarboxylate 1 with triorganosilyl chlorides. The selenone esters 2 are stable towards heat, but labile towards moisture, and are formed via Se‐triorganosilyl selenocarboxylate 3. In the mass spectrometer, isomerization of 2 to its less stable selenol ester 3 takes place, resembling the Schönberg thione‐thiol rearrangement.
Ringschluß zu organosubstituierten Alkalimetall‐2,5‐dihydro‐1,2,5‐oxadiboratolaten[1]
Authors: Köster Roland , Seidel Günter 
Published: July 2007

Ring Formation to Organo‐Substituted Alkalimetal 2,5‐Dihydro‐1,2,5‐oxadiboratolates[1]The organo‐substituted cis‐1,2‐diborylalkenes cis‐Et2BC(Et)C(R′)BR2 (1: R = Et, R′ = Me; 2: R2 = C8H14, R′ = Me; 3: R,R′ = Et; 4: R2 = C8H14, R′ = Et; 5: R = Ph, R′ = Et; 6: R = Et, R′ = Ph), prepared from Na[Et3BCCR′] and R2BCl, react with alkali metal hydroxides MOH (M = Na, K) in toluene to form the corresponding 1:1 addition compounds (M‐7 to M‐12) quantitatively. On heating to ⩾ 100°C of M‐7, M‐9, and M‐12 1 mol of ethane is split off to yield the salts and with regioisomeric anions [M‐13/M‐iso13: R = Et, R′ = Me; M‐15: R,R′ = Et; M‐19/M‐iso19: R = Et, R′ = Ph) of not yet identified structures. Heating of M‐8 and M‐10 yields the salts (M‐14: R = Me; M‐16: R = Et), whereas M‐11 gives the two salts (M‐17) and (M‐18).
Dithiocarbonsäuren und Derivate aus Carbonsäureestern und Lactonen mit dem Organoborsulfid‐Reagenz (9‐BBN)2S
Authors: Köster Roland , Kucznierz Ralf , Seidel Günter , Betz Peter 
Published: July 2007

Dithiocarboxylic Acids and Derivatives from Carboxylic Esters and Lactones with the Organoboron Sulfide Reagent (9‐BBN)2S[1]Bis(1,5‐cyclooctanediylboryl) sulfide (1) reacts with carboxylic esters to give the dithiocarboxylic 1,5‐cyclooctanediylboryl esters 2a–f in high yields (2a: X‐ray crystal structure analysis). Methanolysis of 2a–f leads to the dithiocarboxylic acids 5a–f, which form the corresponding piperidinium salts in the presence of piperidine. When cyclic esters (γ‐, δ‐lactones) are allowed to react with 1, the boryloxy‐substituted dithiocarboxylic 1,5‐cyclooctanediylboryl esters 3a–c are obtained.
Übergangsmetallkomplexe von Diazenen, XXX. Zur Photoreaktion von Octacarbonyl‐dimetallaheterocyclen mit Bis(phosphanen)
Authors: Kisch Horst , Holzmeier Peter , Knoch Falk 
Published: July 2007

Transition Metal Complexes of Diazenes, XXX[1]. – On the Photoreaction of Octacarbonyl Dimetallaheterocycles with Bis(phosphanes)*Irradiation of (CO)4Cr(μ‐pmd)2Cr(CO)4 (1) (pmd = 3,3‐penta‐methylenediazirine) in the presence of bis(dimethylphosphanyl)methane (dppm) affords (CO)3(μ‐pmd)2(μ‐dppm)Cr(CO)3 (2b) and (CO)4Cr(μ‐pmd)(μ‐dppm)Cr(CO)4 (3b) which both contain boat‐like dimetallaheterocyclic rings as indicated by X‐ray analysis. Contrary to that, in the presence of cis‐1,2‐bis(diphenylphosphanyl)ethene the reaction affords the known Cr(CO)4(cdpe) (4c) by complete cleavage of the dimetalla‐heterocycle.
Isocyanid‐ und Heteroallen‐verbrückte Metallkomplexe, VIII. Dieisenkomplexe mit Acylisocyanid‐ und Iminoacylisocyanid‐Brückenliganden
Authors: Fehlhammer Wolf Peter , Schröder Andreas , Sperber Wilfried , Fuchs Joachim 
Published: July 2007

Isocyanide‐ and Heteroallene‐Bridged Metal Complexes, VIII[1,2]. – Diiron Complexes with Bridging Acyl Isocyanide and Iminoacyl Isocyanide LigandsAcylation (aroylation, carbamoylation, imino acylation) of the terminal cyano ligand in Na[Fe2(CN)Cp2(CO)3] (1) leads to the acyl isocyanide (aroyl, carbamoyl, iminoacyl isocyanide)‐bridged neutral complexes [Fe2Cp2{μ‐CNC( = O)R}(CO)3] (2a–i) and [Fe2Cp2{μ‐CNC( = NPh)Ph}(CO)3] (3). An X‐ray structure analysis has been carried out of the pentafluorobenzoyl isocyanide complex 2 f, important results of which are the cis configuration of the complex, the 163.7° puckering of the central Fe2(μ‐C)2 rhomboid, short [1.892(5), 1.911(5) Å] Fe–μ‐C distances to the acyl isocyanide ligand, the nonplanarity of the latter and the 132° bend at the isocyano nitrogen. The contribution of a μ2‐2‐azaallenylidene form is assumed to explain the bonding.