Abstract Diazo compounds are useful synthetic intermediates in organic synthesis but, due to their toxicity and unpredictable explosive behaviour, unique reactivity has not been fully exploited use on large scale avoided. We have developed a reliable method that generates diazo situ. Our approach is based the Bamford–Stevens reaction, which utilizes tosylhydrazone salts as precursors. In presence of phase‐transfer‐catalysts (PTC), we found can be cleanly converted under mild reaction...

Tosylhydrazones derived from aryl aldehydes react with t-BuOK, ClFeTPP, (MeO)3P, and to furnish olefins high E selectivity. These reactions occur through a Wittig-type pathway via the corresponding diazo compounds, metal carbenes phosphorous ylides, water-soluble trimethyl phosphate as byproduct. Similar can also be performed using ethyl diazoacetate; however, selectivity was only observed in presence of LiBr. In this case, reaction is believed phosphonate anion, formed an Arbuzov reaction....

Humic substances are a heterogeneous class of moderate molecular weight, yellow-colored biomolecules present in all soils, sediments, and natural waters. Although humic generally resistant to microbial degradation under anaerobic conditions, some microorganisms soils sediments can use quinone moieties as electron acceptors. Laboratory experiments have shown that act shuttles the reduction ferric iron. Field studies shuttling processes been constrained by lack methods characterize oxidation...

trans-(DMPE)(2)Ru(H)(NH(2)) (1) dehydrogenates cyclohexadiene and 9,10-dihydroanthracene to yield benzene (or anthracene), (DMPE)(2)Ru(H)(2), ammonia. Addition of fluorene 1 results in the formation ion pair [trans-(DMPE)(2)Ru(H)(NH(3))(+)][A(-)] (A(-) = fluorenide, 4a). Complex also reacts with weak acids A-H (A-H phenylacetylene, 1,2-propadiene, phenylacetonitrile, 4-(alpha,alpha,alpha-trifluoromethyl)phenylacetonitrile, cyclobutanone, phenol, p-cresol, aniline) form ammonia...

A series of low-coordinate tin and lead cationic complexes have been synthesized using the bulky β-diketiminate ligand [{N(2,6-iPr2C6H3)C(Me)}2CH]− (BDI) to stabilize metal center. Two different routes [(BDI)Sn]+[X]− [(BDI)Pb]+[X]− were explored (X = B(C6F5)4, AlCl4, MeB(C6F5)3): abstraction chloride with a Lewis acid from (BDI)SnCl (BDI)PbCl methyl group borane (BDI)SnMe (BDI)PbMe. The crystal structures cations determined; in both, solvent molecules found coordinate In case...

We confirm that the μ-oxo species (NON Dipp )Al(μ-O)M(BDI Mes ) are viable intermediates in conversion of CO 2 to carbonate promoted by bimetallic Al–Mg and Al–Zn compounds.

The synthesis of a new potassium gallyl system, K[Ga(NON)] ([NON]2- = [O(SiMe2NDipp)2]2-, Dipp 2,6-iPr2C6H3), has been reported, and its reactivity toward variety ketones studied. is initially isolated as the contacted dimeric pair (CDP) [K{Ga(NON)}]2 but can be converted to monomeric ion (MIP) (NON)Ga-K(TMEDA)2 or separated (SIP) [K(222-crypt)][Ga(NON)] upon addition coordinating polydentate ligands. reaction CDP with two equivalents benzophenone 9-fluorenone per gallium center generates...

Heavy alkaline earth and heterobimetallic s-block “ate” complexes.

The reaction of the potassium aluminyl K[Al(NON)] ([NON]2– = [O(SiMe2NDipp)2]2–, Dipp 2,6‐iPr2C6H3) with stannylene Sn[N(SiMe3)2]2 in benzene afforded K3[(Sn4){Al(NON)}2{N(SiMe3)2}], containing a distorted tetrahedral Sn4‐cluster. Computational analysis indicates that four edges this unit are composed Sn–Sn bonds, remaining two spanned by aluminium involved three centre electron (3c2e) Sn–Al–Sn bonds. formation Al(II) species during is indicated isolation dialuminated cyclohexadiene...

Humic substances were extracted from the sediments of two small alpine lakes in Colorado Front Range and characterized by three-dimensional fluorescence spectroscopy. The index (FI), defined as ratio emitted at 450 nm to that 500 an excitation wavelength 370 nm, was computed thereafter compared additional sediment proxies recent environmental change. Stratigraphic changes both C:N ratios diatom assemblages parallel those FI, together indicating pronounced increases contribution autochthonous...

The chemistry of β-diketiminate germanium alkoxide complexes has been examined and shown to be in sharp contrast its heavier congeners. For instance, (BDI)GeOR (BDI = [{N(2,6-(i)Pr(2)C(6)H(3))C(Me)}(2)CH], R (i)Pr, (s)Bu, (t)Bu) does not react with carbon dioxide form a metal carbonate complex. Addition aliphatic electrophiles, such as methyl iodide or triflate, results the net oxidative addition germanium, giving cationic tetravalent complexes, [(BDI)Ge(Me)OR][X] (X I, OTf). An examination...

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTReactivity of a Parent Amidoruthenium Complex: A Transition Metal Amide Exceptionally High BasicityJ. Robin Fulton, Marco W. Bouwkamp, and Robert G. BergmanView Author Information Department Chemistry, University California Berkeley, 94720 Cite this: J. Am. Chem. Soc. 2000, 122, 36, 8799–8800Publication Date (Web):August 23, 2000Publication History Received12 May 2000Published online23 August inissue 1 September...

A rapid and versatile method for the preparation of planar chiral [2.2]paracyclophane-derived pyridines pyridine N-oxides is reported. The potential utility these compounds in Lewis base catalysis briefly introduced.

A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR2) (M = Ge, Sn, Pb; BDI CH{(CH3)CN-2,6-iPr2C6H3}2; R Ph, Cy, SiMe3) have been synthesized. Two different conformations (endo and exo) are observed in the solid-state; complexes with an endo conformation a planar coordination geometry at phosphorus Sn; whereas possessing exo pyramidal phosphorus. Solution-state NMR studies reveal through-space scalar coupling between tin isopropyl groups on N-aryl moiety ligand,...

A series of beta-diketiminate lead halide complexes has been synthesised LPbCl (2), LPbBr (3) and LPbI (4) (L = {N(2,6-(i)Pr(2)C(6)H(3))C(Me)}2CH]), which includes a rare example three-coordinate iodide (4). The chloride bromide complexes, 2 3, are relatively stable in both the solid solution states, only slowly decomposing to elemental over course month solution, 4 appears be less decomposes after 3 d state at ambient temperatures. complex was treated with KN(SiMe3)2 yield an unusual...

A series of terminal lead alkoxides have been synthesized utilizing the bulky beta-diketiminate ligand [{N(2,6-(i)Pr(2)C(6)H(3))C(Me)}(2)CH](-) (BDI). The nucleophilicities these examined, and unexpected trends were observed. For instance, (BDI)PbOR reacts with methyl iodide only under forcing conditions yet readily, but reversibly, carbon dioxide. degree reversibility is strongly dependent upon minor changes in R group. when = isopropyl, observed resulting alkyl carbonate treated other...

A series of terminal tin(II) alkoxides have been synthesized utilizing the bulky β-diketiminate ligand [{N(2,6-(i)Pr(2)C(6)H(3))-C(Me)}(2)CH] (BDI). The nucleophilicities these examined, and unexpected trends were observed. For instance, (BDI)SnOR only reacts with highly activated aliphatic electrophiles such as methyl triflate, but reversibly carbon dioxide. Both rate reaction degree reversibility is dependent upon minor changes in alkoxide ligand, bulkier tert-butoxide displaying slower...

We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes 2,4,6-Me3C6H2, Dipp 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above −30 °C, while [(HMDS)2Ge═NDipp] engages in intramolecular reaction at 60 °C. [(HMDS)2Ge═NMes] was shown to rearrange via a 1,3-silyl migration give [(HMDS){(SiMe3)(Mes)N}Ge(NSiMe3)] 1:7 equilibrium mixture room temperature. These latter react with unsaturated polar substrates such as...

Reduction of a bis(amidodimethyl)disiloxane Mg( ii ) compound affords mixture N , - and O -chelated i species. Reactivity with RNCNR CO demonstrate reducing behaviour, the products showing combination ligands at magnesium.

The reaction of Cp2Zr(μ-N-tBu)IrCp* (1) with nitriles (RC⋮N) yields the cyclometalated species Cp2Zr(μ-N-tBu)(μ-NC(H)(R)CH2-η5-C5Me4)Ir (R = C6H5 (2a), o-Et-C6H4 (2b), (p-CH3)C6H4 (2c), (p-CF3)C6H4 (2d), (p-MeO)C6H4 (2e), cyclopropyl (2f), CH(Me)2 (2g), NC(CH2)3 (2h)). An intermediate is observed in 1 cyanocyclopropane. This has been characterized by NMR spectroscopy as a tetramethylfulvene complex bridging alkylidene−amido moiety, Cp2Zr(μ-N-tBu)(μ-NCRH)(η5-C5Me4CH2)Ir cyclopropyl; 3)....

The β-diketiminatolead(II)-amido and -anilido complexes, [(BDI)Pb(NRR′)] (BDI = [{N(2,6-iPr2C6H3)C(Me)}2CH]; NRR′ NH(2,6-iPr2C6H3), N(iPr)2), react at the amido/anilido nitrogen atom with simple saturated electrophiles such as methyltriflate. Addition of unsaturated to these complexes either results in formation a complex mixture products, or case phenylisocyanate, reaction γ-carbon β-diketiminato ligand form that is net result nucleophilic attack by electrophilic carbon centre...

Addition of MesN3 (Mes=2,4,6-Me3 C6 H2 ) to germylene [(NONtBu )Ge] (NONtBu =O(SiMe2 NtBu)2 (1) gives germanimine, )Ge=NMes] (2). Compound 2 behaves as a metalloid, showing reactivity reminiscent both transition metal-imido complexes, undergoing [2+2] addition with heterocumulenes and protic sources, well an activated diene, [4+2] cycloaddition, or "metallo"-Diels-Alder, reaction. In the latter case, diene includes Ge=N bond π-system Mes substituent, which is reactive towards dienophiles...