bluuebunny/crossref_metadata_2025_split huggingface dataset:
Contributions to the Chemistry of Boron, 214. Synthesis and Reaction Chemistry of Aminophosphanylboranes
Authors: Dou Danan , Westerhausen Matthias , Wood Gary L. , Duesler Eileen N. , Paine Robert T. , Linti Gerald , Nöth Heinrich 
Published: July 2007

AbstractAminochlorophosphanylboranes, (R2N)B(Cl)P(SiMe3)2 (1a — d) and (R2N)B(Cl)PH2 (2a — d), are obtained from elimination reactions between aminochloroboranes and LiP(SiMe3)2 and LiPH2, respectively. Selected reaction chemistry of (i1‐Pr2N)B(Cl)P(SiMe3)2] (1a) with NH3, Me3SiN3, Cr(CO)5 · NMe3, and W(CO)5 · NMe3 is described. The azide (i1‐Pr2N)B(N3)P(SiMe3)2 (12a) is stable at 25°C; however, thermolysis at 80°C provides a novel six‐membered ring compound [(i1‐Pr2N)BN(SiMe3)P(SiMe3)]2 (13a). The reaction of (Ph2N)B(Cl)P(SiMe3)2 (1b) with LiP(SiMe3)2 produces the only isolable bis(phosphanyl)borane (5b), while combination of (R2N)B(Cl)Ph2 with LiPH2 · DME yields new diphosphadiboretanes 6 {(R2N)BPH}2 (R2Ni1‐Pr2N, Ph2N and tmp2,2,6,6‐tetramethylpiperidino) and triphosphatriborinanes 7 {(R2N)BPH}3 (R2N(Me3Si)2N, Me2N and Et2N). Two salts, [(i1‐Pr2N) DME]2 (8a) and [tmpLi · DME]2 (8c) (DMEethylene glycol dimethyl ether) are also isolated. The results of molecular structure determinations for [(i1‐Pr2N)Bn(SiMe3)P(SiMe3)]2 (13a), [tmpBPH]2 (4c), [tmpBPH]2 · Cr(CO)5 (7c), {[(Me3Si)2N]BPH}3 (4d), {[(Me3Si)2N]BPH}3 · Cr(CO)5 (7d), (Ph2N)B[P(SiMe3)2]2 (5b), and [(i1‐Pr2N) · DME]2 (8a) are discussed.
Bis(pentamethylcyclopentadienyl)keton und ‐thioketon: Kohlenstoff‐Verbindungen mit präformierter Diels‐Alder‐Geometrie
Authors: Jutzi Peter , Schwartzen Karl‐Heinz , Mix Andreas , Stammler Hans‐Georg , Neumann Beate 
Published: July 2007

Bis(pentamethylcyclopentadienyl) Ketone and Thioketone: Carbon Compounds with Performed Diels‐Alder Geometry1,2,3,4,5‐Pentamethyl‐1,3‐cyclopentadien‐5‐carbonyl chloride (2) is formed in good yields by the reaction of pentamethylcyclopentadienyllithium (1) with phosgene. The corresponding carbothioyl chloride 3 is synthesized by treatment of 1 with thiophosgene. Both acyl chlorides are stable against air and moisture and difficult to attack in SN2‐type reactions. Treatment of 2 and 3 with trimethyl(pentamethylcyclopentadienyl)stannane in the presence of boron trifluoride — ether leads to bis(1,2,3,4,5‐pentamethyl‐1,3‐cyclopentadien‐5‐yl) ketone (5) and thioketone (6), respectively. Even at room temperature, 5 and 6 tend to intramolecular [4 + 2] cycloaddition reactions. X‐ray crystal structure investigations of 2, 5, and 6 show the steric demand of the pentamethylcyclopentadienyl ligand and explain the untypical chemical behavior of 2 and the easy [2 + 4] cycloaddition reactions of 5 and 6.
(Diphenylphosphanyl)(tetramethylcyclopentadienyl)thallium(I)
Authors: Schumann Herbert , Ghodsi Tahereh , Esser Lothar , Hahn Ekkehard 
Published: July 2007

(Diphenylphosphanyl)(tetramethylcyclopentadienyl)thallium(I)(Diphenylphosphanyl)tetramethylcyclopentadiene (1) reacts with TlOC2H5 to form Tl[C5Me4PPh2] (2). In a transmetallation reaction 2 reacts with InCl to yield the corresponding In[C5Me4PPh2] complex (3). The 1H‐, 13C‐NMR‐and mass spectra as well as the single‐crystal X‐ray structure analysis of the monomeric 2 are reported and discussed.
Preparation and Crystal Structures of Gold(I) Complexes of a Series of Benzenethiolates: Pair Formation by Gold‐to‐Gold Interactions of (Benzenethiolato)(triphenylphosphane)gold(I)
Authors: Nakamoto Masami , Hiller Wolfgang , Schmidbaur Hubert 
Published: July 2007

AbstractChloro(triphenylphosphane)gold(I) reacts readily with benzenethiol C6H5SH and a series of sterically hindered (2,4,6‐trialkylbenzene)thiols 2,4,6‐R3C6H2SH in the presence of NEt3 to yield stable gold(I) complexes Ph3PAu(S – 2,4,6‐C6H2R3) [RH (1), Me (2), Et (3), iPr (4)]. The crystal structures of these complexes have been determined by single‐crystal X‐ray diffraction analysis. In all compounds the gold atoms are linearly two‐coordinate with very similar bond lengths and angles. – While complexes 2 – 4 with bulky thiolate ligands are monomeric in the crystal lattice, complex 1 has been found to form pairs of molecules with intermolecular gold – gold contacts of 313.5(5) pm. The Mössbauer spectra of the complexes exhibit large isomer shifts (I.S.), ranging from 3.06 to 3.72 mm s–1, and quadrupole splittings (Q.S.), ranging from 7.90 to 8.68 mm s–1. These data can be attributed to the strong electron‐donating properties of the benzenethiolate ligands. The gold – gold contacts in complex 1 lead to I.S. and Q.S. values which are slightly smaller than those of 2 – 4. The Au – S distances do not show a major influence of the S – Au – P pairing in complex 1 as compared to complexes 2 – 4.
Beiträge zur Chemie des Bors, 215. Darstellung und Reaktionen monomerer Tetraorganylphosphanylborane
Authors: Nöth Heinrich , Staude Siegfried , Thomann Martina , Paine Robert T. 
Published: July 2007

Contributions to the Chemistry of Boron, 215[1]. – Synthesis and Reactions of Monomeric Tetraorganyl‐phosphanyl‐boranesThe reaction of diorganyl‐chloroboranes with lithium diorganyl‐or lithium bis(trimethylsilyl)phosphides leads to the monomeric phosphanylboranes tBu2BPtBu2 (1), tBu2BP(SiMe3)2 (2), 9‐BBNPtBu2 (3), 9‐BBNP(SiMe3)2 (4), and Cy2BPtBu2 (5). These species were studied by NMR‐spectroscopic methods. For further characterization reactions of the compounds 1, 3, and 5 have been investigated. Heating of 1 and 5 results in the formation of the dimeric phosphanylboranes tBu(H)BPtBu2 (8) and Cy(H)BPtBu2 (9) by dehydroboration. Dimers 8 and 9 are present as cis‐ and trans1‐isomers as confirmed by X‐ray structure analyses. The trans1‐isomer of 9 shows a planar (BP)2 four‐membered ring, whereas the ring of the cis1‐isomer of 8 is slightly folded. Furthermore, the reaction of 3 with 9H‐9‐BBN yields (μ1‐H)(μ‐tBu2P)[9‐BBN]2 (14), whose bridged structure is proven by a crystal structure analysis. Oxidation of the phosphorus atom in 3 with sulfur leads to the S1‐boryl thiophosphinate tBu2(S)PS‐9‐BBN (16).
Nucleophile Singulett‐Carbene in der [4 + 1]1‐Cycloaddition mit 1,2,4,5‐Tetrazinen: Eine neue Isopyrazol‐Synthese
Authors: Gerninghaus Christian , Kümmell Andreas , Seitz Gunther 
Published: July 2007

Nucleophilic Singlet Carbenes in the [4 + 1] Cycloaddition with 1,2,4,5‐Tetrazines: a New Synthesis of IsopyrazolesA series of 3,6‐disubstituted 1,2,4,5‐tetrazines 6, including C6H5, SCH3, SO2CH3, N(CH3)2, CF3, CO2CH3 groups, has been submitted to [4 + 1] cycloaddition with the nucleophilic singlet carbenes 4, 15, and 20, which are generated from the precursors 1, 11 and 19, resp. In all cases isopyrazoles (4H1‐pyrazoles) 9, 10, 18, and 21 are isolated in good yields. They are formed in a two‐step reaction sequence with the [4 + 1] cycloadducts of type 8 as intermediates which eliminate nitrogen by subsequent [4 + 2] cycloreversion. The acceptor‐substituted isopyrazole 9e is characterized as an electron‐deficient diene by some Diels‐Alder reactions with inverse electron demand leading to the expected azo‐bridged cycloadducts 23, 25, 27, 29, and 31 without acid catalysis or application of higher pressure. With cyclooctyne (32), the [4 + 2] cycloaddition is followed by a [4 + 2] cycloreversion with formation of the cyclopentacyclooctene 34.
Rearrangements of 1‐ and 2‐Cyano‐2‐norbornyl Cations
Authors: Geier Holger , Kautz Cornelia Brigitte , Kirmse Wolfgang , Landscheidt Heinz , Schimpf Iris , Siegfried Rainer 
Published: July 2007

AbstractSulfonates of exo‐2‐hydroxynorbornane‐endo‐2‐carbonitrile (2c–e) were found to rearrange exothermally to give sulfonates of exo‐2‐hydroxynorbornane‐1‐carbonitrile (6c–e), solvolysis being a minor side reaction. In contrast, the analogous endo substrates (3c–e) afforded the rearranged alcohol 6a and tricyclo[2.2.1.02,6]heptane‐1‐carbonitrile (4) as the major products. We have not been able to trap 2‐cyano‐2‐norbornyl cations by external nucleophiles or by internal 6,2‐shifts of hydrogen or carbon. On the other hand, there is good evidence for the generation of 1‐cyano‐2‐norbornyl cations from both 3d, e and 6e. The degenerate 6,2‐H shift in these species has been uncovered by means of labeled or optically active precursors. The 1‐CN substituent clearly promotes the 6,2‐H shift relative to the parent 2‐norbornyl cation, but is inferior to 1‐C2F5. Ring expansion of a spiroannelated cyclopropane, involving a 6,2 shift of carbon, was also observed (25, 26 → 27, 28). Our data strongly suggest that 2‐cyano‐2‐norbornyl cations are less stable than 1‐cyano‐2‐norbornyl cations. The reaction rates of 2c versus 6c do not reflect the stability of the incipient carbocations, owing to the large difference in ground state energy.
Tin for Organic Synthesis, 7. New Regioselective Syntheses of Diaryl Sulfones, Arenesulfonamides, and Arenesulfonic Acid Sodium Salts
Authors: Neumann Wilhelm P. , Wicenec Christian 
Published: July 2007

AbstractThe reaction of (trialkylstannyl)arenes 1 with corresponding reagents containing a chlorosulfonyl group leads, by exclusive ipso substitution, to important diaryl sulfones 2a – i, N1‐alkyl‐arenesulfonamides 8a – f, and sodium arenesulfonates 13a – c in high yields under mild conditions. The specific leaving ability of the stannyl group allows, moreover, the preparation of arylsulfonyl isomers which are not accessible under the influence of the conventional directing forces of substituents. With N, N1‐dialkylamidosulfonyl chloride/AlCl3 complexes no destannylation takes place, but the first intramolecular sulfonyltin complex 11 is formed. This result is used to discuss details of the mechanism involved.
Cycloadditionen von 6H‐1,3,4‐Oxadiazin‐6‐onen (4,5‐Diaza‐α1‐pyronen), 12. Dieckmann‐Kondensationen ohne Basen
Authors: Christl Manfred , Lanzendörfer Ulrike , Grötsch Maria M. , Hegmann Joachim , Ditterich Elke , Hüttner Gerhard , Peters Eva‐Maria , Peters Karl , Von Schnering Hans Georg 
Published: July 2007

Cycloadditions of 6H‐1,3,4‐Oxadiazin‐6‐ones (4,5‐Diaza‐α1‐pyrones), 12[1]. – Dieckmann Condensations without BasesPrepared by treatment of methyl 6‐oxo‐5‐phenyl‐6H‐1,3,4‐oxadiazine‐2‐carboxylate (1) with norbornene, norbornadiene, and styrene, respectively, the γ1‐oxoketenes 2, 5, and 7 were allowed to react with methanol. Inter alia, the semiacetals 3, 6, and 10 of 1,2‐cyclopentanedione derivatives were formed. The identity of 3 has been established by an X‐ray structure analysis. The pathway to these compounds seems to be closely related to the mechanism of the Dieckmann condensation. By using [D4]methanol, it has been shown that the semiacetal methoxy group underwent an intramolecular [1,2] migration. Methanol was eliminated from semiacetal 10 by chromatography on silica gel with formation of the enol 11. In addition to 3 and 10, the dimethyl adipates 4 and 9 were observed as the expected methanolysis products of the γ1‐oxoketenes 2 and 7, respectively. The diesters 9 were obtained on a second route from 7. Treatment of 7 with trifluoroacetic acid and subsequent hydrolysis gave rise to the monoesters 12, which were converted into the diesters 9 by conventional esterification.
Monoazadien‐Komplexe elektronenarmer Übergangsmetalle, I. Zirconocen(1‐aza‐1,3‐dien)1‐Komplexe: Synthese, Struktur und Reaktionen
Authors: Scholz Joachim , Nolte Matthias , Krüger Carl 
Published: July 2007

Monoazadiene Complexes of Electron‐Deficient Transition Metals, I. – Zirconocene(1‐aza‐1,3‐diene) Complexes: Synthesis, Structure and Reactions[1]The reduction of Cp2ZrCl2 in THF by Mg in the presence of 1‐aza‐1,3‐dienes 2a–d generates the orange air‐sensitive zirconocene(s‐cis‐1‐aza‐1,3‐diene) complexes 3a–d. 1H‐and 13C‐NMR spectral data of 3a–d indicate that the bonding of the heterodiene ligand has σ2,π1‐metallacyclopentene rather than η4‐1‐aza‐1,3‐diene character. No evidence for s‐trans1‐heterodiene coordination was found in any of the new zirconocene complexes. The molecular structure of 3d has been determined by single‐crystal X‐ray diffraction, confirming the envelope‐shaped σ2,π1‐type structure also in the solid state. 3b slowly reacts with one molar equivalent of acetophenone to give a seven‐membered oxaazametallacycle (4) which has a cis1‐CC bond in the ring. The structure of 4 has been determined by NMR and X‐ray diffraction.
1,3‐Donor/Donor‐substituierte Allene, VII Allencarboxanilide durch Umallenierung oder [2.3]/[3.3]1‐sigmatrope Umlagerungen Bausteine mit vielseitigem intra‐und intermolekularem Synthesepotential
Authors: Saalfrank Rolf W. , Bauer Udo , Hilbig Klaus , Welch Andreas 
Published: July 2007

1,3‐Donor/Donor‐Substituted Allenes, VII[1]. – Allenecarboxanilides by Transallenation or [2.3]/[3.3]1‐Sigmatropic Rearrangements – Building Blocks with Versatile Intra‐and Intermolecular Synthetic PotentialHerrn Professor Richard P. Kreher zum 60. Geburtstag gewidmet.
The reaction of 1,3‐bis(alkylarylamino)1‐1,3‐diethoxyallenes 1,2 with disubstituted malonyl chlorides 3 leads to N, N′1‐dialkyl‐N, N′1‐diarylallene‐1,1‐dicarboxamides 4, 5, and 2H1‐pyran‐2,4(3H)1‐diones 6, 7, respectively, with a transallenation reaction being favoured in the case of allene 1. Thermal tandem cyclisation of allene‐1,1‐dicarboxanilide 4c via 2‐quinolone 8 affords phenanthridone 9. Spontaneous acylcycloalkane/cycloenol ether isomerisation of spirane 6b gives pyrane 12. Thermally induced (Z)1‐anilinoacryclic acid/quinolone cyclisation of pyranes 6a, 12, and 7 leads to 4‐quinolones 11, 13, and 14. Propargyl THP ether 15 reacts with carbamoyl chloride 16 to yield alkinol‐N1‐phenylanilides 17. Alkinol 17a reacts with sulfinyl chloride 18 to yield sulfinic ester 19, which on heating undergoes a [2.3]1‐sigmatropic rearrangement to N1‐phenyl‐1‐sulfonylallene‐1‐carboxanilide 20. Reaction of alkinols 17 with sulfenyl chlorides 21 or chlorophosphanes 23, followed by [2.3]1‐sigmatropic shift, affords N1‐phenyl‐1‐sulfinyl‐22 and N1‐phenyl‐1‐phosphorylallene‐1‐carboxanilides 24, respectively. Alkinyl ketene acetal intermediates 26 are formed starting from alkinol 17a and orthoesters 25. Spontaneous [3.3]1‐sigmatropic rearrangement of 26 gives N1‐phenylallene‐1‐carboxanilides 27. Intramolecular Diels‐Alder (IDA) reactions of the allene‐1‐carboxanilides 27 lead to [2.2.2]bicycles 28. Contrarily, the IDA intermediates of 20b and 24 further isomerize to the [3.2.1] bicycles 29 and 30. The allenyl sulfoxides 22 readily undergo Michael‐type reactions with CH‐acidic compounds 31 to give allyl sulfoxides 32. Among these, only 32d can be isolated, whereas 32a–c spontaneously rearrange in a four‐step reaction cascade to butenolides 33a–c. A Michael‐type reaction of (diethoxyphosphoryl)allenes 24 with α1‐hydroxy ketones 34 followed by a Horner‐Emmons reaction leads to alkylidene‐dihydro‐furans 35, which isomerize in the presence of a base to yield furans 36. Analogously, allenes 24 react with 2‐hydroxybenzaldehydes 37 or 2‐pyrrole‐/2‐imidazole derivatives 40 to form alkylidenechromenes 38 and pyrrolizines/pyrroloimidazoles 41, respectively. Benzopyrylium salts 39 are accessible from chromenes 38 and perchloric acid.
Siderophore, III. Neutrale Koordinationspolymere aus Pyrrolinyl‐enolen und Kupfer(II)1‐acetat durch spontane Selbstorganisation – Kristallstruktur von 2D‐[CuL22]n
Authors: Sallfrank Rolf W. , Struck Oliver , Peters Karl , Von Schnering Hans Georg 
Published: July 2007

Siderophores, III[1]. – Neutral Coordination Polymers from Pyrrolinyl Enols and Copper(II) Acetate by Spontaneous Self‐Assembly – Crystal Structure of 2D‐[CuL22]nContrary to tetrazole 1 (HL1) structurally analogous pyrrolidines 3 (HL2) react with copper(II) acetate to give 2D‐coordination polymers 4 ([CuL22]n), rather than 3D‐coordination polymer 2 ([CuL21]n). The structure of 4a is established by single‐crystal X‐ray diffraction. The formation of 2D‐coordination polymer 4a is understandable if 3a or its enolate is considered as tridentate chelate ligand and if an intermediate formation of the coordinatively unsaturated copper(II) building block 5a is assumed. The monomers 5a are bidentate coordinating with the two CN groups, which leads to linking of monomers and to coordinative saturation at the copper(II) center of 5a with formation of 2D‐4a. Depolymerisation of 2D‐4 with excess pyridine leads to racemic mononuclear tetragonally pyramidally coordinated copper(II) chelate complexes 6 (X‐ray), whereas under the same conditions 3D‐2 yields octahedral bis(pyridine) complex CuL21(Py)2.
Metallorganische Lewis‐Säuren, IL. Bis(acyl)1‐verbrückte heterometallische Komplexe von Rhenium, Molybdän, Ruthenium und Kupfer
Authors: Lippmann Elisabeth , Robl Christian , Beck Wolfgang , Berke Heinz , Kaesz Herbert D. 
Published: July 2007

Organometallic Lewis Acids, IL[1]. – Bis(acyl)1‐Bridged Heterometallic Complexes of Rhenium, Molybdenum, Ruthenium, and CopperThe reaction of the metalla‐β1‐diketonate complex [(OC)41‐Re[–C(Me)O]2][NMe4] with various organometallic Lewis acids yields the bis(acyl)1‐bridged bimetallic complexes (OC)4 ‐Re[–C(Me)O–]2Re(CO)4 (1), (OC)4Re[–C(Me)O–]2MoCp(CO)2 (2), (OC)4Re[–C(Me)O–]2Ru(η31‐C3 H5)(nbd) (nbdnorbor‐nadiene) (3), [(OC)4 Re[–C(Me)O–]2Ru(PPh3)2 (CO)2][BF4] (4), and (OC)4 Re[–C(Me)O–]2Cu[–O(Me)C–]2Re(CO)4 (5), respectively. The structures of the compounds 1–5 have been determined by X‐ray diffraction. They show different conformations of the six‐membered ring Re[–C(Me)O–]2[M]. The molecular structure of complex 1 proves a “flipping” of the acyl ligands.
Trimethylsilylcyanid als Umpolungsreagens, XXIII. Umpolungsprodukte aus α,β1‐ungesättigten Aldehyden mit α,β1‐ungesättigten Carbonyl‐Verbindungen: Folgereaktionen
Authors: Hünig Siegfried , Schäfer Matthias , Schweeberg Walter 
Published: July 2007

Trimethylsilyl Cyanide – A Reagent for Umpolung, XXIII[1]. – Products from Umpolung of α,β1‐Unsaturated Aldehydes and α,β1‐Unsaturated Carbonyl Compounds: Consecutive ReactionsThe unsaturated nitrile 1 is transformed by TiCl4 into chloronitrile 2, whereas reaction with [BzNMe3]+F− and treatment with acids yields cyanocyclopentenone 4. Removal of the umpolung groups from 1 and 5–8 by [BzNMe3]F− results in the unsaturated 1,4‐diketones 9–13 only if the cyanide ions formed are prevented by ZnO from adding to the double bond. Condensation of ketones 9 and 11–13 with tBuOK yields cyclopentenones 14–18 with conjugated vinylic groups. In the presence of [BzNMe3H]+F− α1‐cyano enol silyl ethers 22–24 are smoothly converted in methanol into ϵ1‐oxo‐carboxylic esters 19–21, whereas in pure methanol α1‐hydroxycyclopentanecarboxylic esters 25–27 are produced in high yied.
Maßgeschneiderte Wirtverbindung für Piperazin und verwandte Amine
Authors: Hoss Ralf , Vögtle Fritz 
Published: July 2007

Tailor‐Made Host for Piperazine and Related AminesThe 38‐membered bis‐catechol 4b is obtained by cyclisation of the diacyl dichloride 3c with the diamine 2b in 45% yield, whereas a 68‐membered octalactam 7 is formed under similar conditions from 5 and 1b. Bis‐catechol 4b is a selective host compound for piperazine (8) and the structurally related diamine 9. Association constants for the 1:1 complexes have been measured by 1H‐NMR titration experiments. A nucleobase guest (pterine, 24) was extracted into a hydrochloric acid phase by complex formation with the host 4b. The results are compared with solubility and transport experiments obtained by use of analogous macrobicyclic tris‐catechol hosts.
Bimolekulare Radikalbildung durch H‐Transfer, 2. H‐Transferreaktionen mit Phenalen
Authors: Gerst Matthias , Rüchardt Christoph 
Published: July 2007

Bimolecular Formation of Radicals by H‐Transfer, 2[1]. – H‐Transfer Reactions of PhenaleneThe uncatalysed H transfer from phenalane (7) to α1‐methyl‐styrene (2) and the selfreaction (d) of phenalene (7) are quantitative transformations in the presence of an excess of 9,10‐dihydroanthracene (1) (DHA) in diphenyl ether at 200–250°C. In this system phenalene (7) is consumed only in reaction (d) because the phenalenyl radicals (9) are captured by DHA (1) to give phenalene (7) and 9,10‐dihydroanthryl radicals (3). The latter disproportionate rapidly. Accordingly, phenalene (7) acts as a catalyst for the hydrogenation of α1‐methylstyrene (2) by DHA (1). The activation parameters of the two reactions (e) and (d) were obtained from kinetic experiments between 200–250°C. They allow the determination of the CH bond enthalpy δHdiss of phenalene (7) (65.3 kcal mol–1) at the methylene position.
Monomere flüchtige Alkoxide von Chrom und Bismut
Authors: Herrmann Wolfgang A. , Huber Norbert W. , Anwander Reiner , Priermeier Thomas 
Published: July 2007

Monomeric Volatile Alkoxides of Chromium and BismuthThe β1‐methoxy alcohol HOCMe2CH2OMe (1) yields monomeric (mononuclear), highly volatile and soluble complexes M(OCMe2CH2OMe)3 3a, b of chromium(III) and bismuth(III), respectively, upon treatment with the amide precursors Cr[N(iPr)2]3 (2a) and Bi[N(SiMe3)2]3 (2b). A single‐crystal X‐ray diffraction analysis of 3a was performed because of the novelty of this particular compound being the first thermostable monomeric alkoxide of trivalent chromium. 3a exhibits an octahedral structure with six oxygen atoms surrounding the metal atom. Three chelating O,O′ ligands coordinate to Cr(III) in a mer configuration.
What is Different in Photochemical Reactions of Primary and Secondary Alkylcobaloximes with and without Radical Traps?
Authors: Hartung Jens , Hertel Barbara , Trach Frank 
Published: July 2007

AbstractPhotochemical cyclization and halogen abstraction reactions of secondary alkylcobaloximes1band1dcompared to their primary counterparts1aand1cshow an enhanced reactivity of secondary alkylcobaloximes: Thus, cyclohexylcobaloxime1dreacts 13 times faster with CCl4thann1‐hexylcobaloxime1c, 6‐hepten‐2‐yl‐cobaloxime1brearranges 58 times faster to its cyclopentylmethyl isomer4bthan 5‐hexenylcobaloxime1a. Althoughfreealkyl radicals are reactive intermediates in photolytic conversions of alkylcobaloximes1in organic solvents, the presence of BrCCl3or bromobenzene in photoreactions of primary alkylcobaloximes1aand1cseems to cause a more efficient homolytic cleavage of the Co – C bond.
Preparation and Properties of Alkylbis(dimethylglyoximato)rhodium(III) Complexes
Authors: Giese Bernd , Kesselheim Christoph , Hartung Jens , Lindner Hans Jörg , Svoboda Ingrid 
Published: July 2007

AbstractPrimary, secondary, and tertiary alkylrhodoximes 1 were prepared from alkyl bromides and tosylates 4 and the trans1‐dichlororhodium complex 3. X‐ray crystallography of the previously unknown tert1‐butylrhodoxime 1k reveals structural features of this tert‐s̀1‐alkylrhodium compound. Photochemical homolytic cleavage of the Rh – C bond in alkylrhodoximes 1 only occurs in the presence of efficient radical traps which allow further mechanistic studies.
Ligand‐Induced Hydrogen Scrambling and Interligand Carbon – Carbon Bond Formation in the Gas‐Phase Reactions of MCH3+ (MFe, Co) with 1‐Octyne and 1‐Octene
Authors: Schwarz Josef , Schwarz Helmut 
Published: July 2007

AbstractEvidence is presented that the encounter complexes of MCX3+ (MFe, Co; XH, D) with 1‐octyne, prior to C – H‐and C – C bond activation, undergo interligand C – C bond coupling as well as extensive hydrogen exchange. In distinct contrast, in the related complexes formed by gas‐phase reaction of MCX3+ (MFe, Co; XH, D) with 1‐octene, the metal‐methyl group retains its identity while the alkene ligand is subject to extensive hydrogen scrambling presumably by β1‐hydrogen shift to and from the metal centers.