7379-79-5Relevant academic research and scientific papers
Trimethylsilylnitrene and Its Surprising Rearrangement to N-(Dimethylsilyl)methanimine via Silaziridine and Silaazomethine Ylide
Wentrup, Curt,Lüerssen, Holger,Silva, Hugo Santos,Dargelos, Alain,Bégué, Didier
, p. 14547 - 14553 (2018)
Photolysis of trimethylsilyl azide at 254 nm in Ar matrix at 15 K generates the triplet ground state trimethylsilylnitrene 2 aT, observed by ESR spectroscopy (|D/hc|=1.540 cm?1; |E/hc|=0.0002 cm?1). Calculations at the CASPT2(14,13) level reveal the open-shell singlet nitrene 2 aS(1A“) is a discrete intermediate lying ≈38 kcal mol?1 above the triplet. The normally expected rearrangement of the nitrene 2 aS to dimethylsilanimine 3 a has a high calculated barrier (33 kcal mol?1), which explains why this product has never been observed. Instead, the singlet nitrene 2 aS inserts into a methyl C?H bond to yield silaziridine 12 via an activation barrier of only 6 kcal mol?1. Ring opening of 12 generates a 1-silaazomethine ylide 13, in which a facile 1,2-H shift yields N-(dimethylsilyl)methanimine 5, all with barriers well below the energy of the singlet nitrene.
Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation
Pappas, Iraklis,Chirik, Paul J.
, p. 13379 - 13389 (2016/10/22)
The hydrogenolysis of titanium-nitrogen bonds in a series of bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η5-C5Me5)(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl, [Rh]-H) and (η5-C5R5)(CO)3Cr-H ([Cr]R-H, R= H, Me) were evaluated for formal H atom transfer reactivity and were selected due to their relatively weak M-H bond strengths yet ability to activate and cleave molecular hydrogen. Despite comparable M-H BDFEs, disparate reactivity between the two compounds was observed and was traced to the vastly different acidities of the M-H bonds and overall redox potentials of the molecules. With [Rh]-H, catalytic syntheses of ammonia, silylamine and N,N-dimethylhydrazine have been accomplished from the corresponding titanium(IV) complex using H2 as the stoichiometric H atom source. The data presented in this study provides the thermochemical foundation for the synthesis of NH3 by proton coupled electron transfer at a well-defined transition metal center.
Synthesis, properties, and structural investigations of 1,3,2-diazaborolidines and 2,3-dihydro-1H-1,3,2-diazaboroles
Schmid, Günter,Polk, Michael,Boese, Roland
, p. 4421 - 4429 (2008/10/08)
A series of variously substituted 1,3,2-diazaborolidines have been prepared by different methods. 1,3-Diisopropyl-2-methyl-1,3,2-diazaborolidine (1a), 1,3-diethyl-2-methyl-1,3,2-diazaborolidine (2a), 1-ethyl-2,3-dimethyl-1,3,2-diazaborolidine (3a), and 1,2,3-trimethyl-1,3,2-diazaborolidine (4a) are formed from the corresponding lithiated ethylenediamines and CH3BBr2 in diethyl ether (method C). 2-Methyl-1-(trimethylsilyl)-1,3,2-diazaborolidine (5a), 1-tert-butyl-2-methyl-1,3,2-diazaborolidine (6a), and 1-isopropyl-2-methyl-1,3,2-diazaborolidine (7a) can be prepared either by method C, by method A, using the ethylenediamines and H3CB[N(CH3)2]2 to eliminate HN(CH3)2, or by method B, starting with CH3BBr2, NR3, and the corresponding ethylenediamines. The unsaturated 2,3-dihydro-1H-1,3,2-diazaboroles 1b-7b are synthesized by catalytic dehydrogenation in either liquid (1b-3b) or gaseous (4b-7b) state. Diazaboroles can act as 6-π-electron donors in Cr(CO)3 complexes. 1b-4b react with (CH3CN)3Cr(CO)3 under various conditions to form the corresponding complexes 1c-4c. The monosubstituted rings 5b-7b are not suited to form stable Cr(CO)3 complexes. One of the two rings in 8 can be combined with a Cr(CO)3 fragment to give 9. The yellow 1H-1,3,2-diazaborole-tricarbonylchromium complexes 1c-4c decompose slowly at room temperature. 2,3-Dihydro-2-methyl-1,3-bis(trimethylsilyl)-1H-1,3,2-diazaborole (10) can be metalated at one N atom by NaNH2 and K(O-t-Bu) to give the salts 11a and 11b. These alkali-metal derivatives can easily be protonated by HCl or CH3OH to form the N-H derivative 5b. X-ray structure analyses have been performed on the diazaborolidines 2a and 4a and on the diazaboroles 1b, 2b, 4b, and 8. The structures of 2a and 4b have been determined at two different temperatures. 1b, 2b, and 2a crystallize in the monoclinic space groups P21/n, P21/c, and Cc, respectively. 4a crystallizes hexagonally in the space group P32; 4b, tetragonally in the space group P42. X-X-Difference electron densities of 4a, 2a, and 4b show that the B-N bonds in the saturated compounds 4a and 2a possess remarkable double-bond character. The electron distribution in the 1,3,2-diazaborole 4b corresponds with that in 6-π-electron systems.
Vinylthioacetamido oxacephalosporin derivatives
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, (2008/06/13)
A compound of the formula: STR1 wherein u represents hydrogen, carboxamido, N-hydroxycarboxamido, carboxy, azido, an aryl, an acylamino, a protected carboxy or an N-alkoxycarboxamido, or, together with v, can represent --S-- or --CH2 S--; v represents hydrogen, halogen, cyano or an alkylthio, or, together with u, can represent --S-- or --CH2 S--, or, together with w, can represent --(CH2)3 CO--; w represents hydrogen, carboamoyl, cyano, carboxy, an N-alkylcarbamoyl, an alkyl, an aryl, a protected carboxy or a heterocycle, or, together with v, can represents --(CH2)3 CO--; x represents halogen, trifluoromethyl, an alkylthio or an arylthio; y represents hydrogen, a light metal or a carboxylic acid protecting group; and z represents an acyloxy or a heterocycle-thio, each of the above radicals represented by the symbols u, v, w, x, y and z being optionally substituted by halogen or a carbon-, nitrogen-, oxygen- or sulfur-containing functional group, a process for preparing the compound, a pharmaceutical composition containing the compound, and a therapeutical use of the compound. A compound of the formula: STR2 wherein u, v, w and x are as defined above, useful as a starting compound for preparing the compound (I) is also provided.
Oxacephalosporin derivatives
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, (2008/06/13)
A 7β-ureidoacetamido-7α-methoxy-3-[1-(2-hydroxyethyl)-1H-tetrazol-5-yl]thiomethyl-1-dethia-1-oxa-3-cephem-4-carboxylic acid derivative represented by the following formula: STR1 wherein R is aryl or heteroaryl; R1 is hydrogen or alkyl optionally substituted by halogen or pyridinium; R2 is hydrogen or a hydroxy-protecting group; and R3 is hydrogen, a light metal, or a carboxy-protecting group.
Partially Substituted Tetrazenes (Me3E)nN4H4-n (E = Si, Ge, Sn): Preparation, Characterization, and Thermolysis
Wiberg, Nils,Meyers, Rene,Vasisht, Sham Kumar,Bayer, Heiner
, p. 2886 - 2899 (2007/10/02)
Partially substituted tetrazenes (Me3E)nN4H4-n (E = Si, Ge, Sn) can be prepared by protolysis of higher substituted tetrazenes (Me3E)oN4H4-o (o > n) or by silylation, germylation, or stannylation of lower substituted tetrazenes (Me3E)mN4H4-m (m 140 deg C1/2 = 3/4 h), of (Me3Si)2N-N=N-NH2 to Me3SiN3 and Me3SiNH2 (concentrated solution; τ40 deg C1/2 ca. 1/4 h), and of (Me3Si)HN-N=N-NH(SiMe3) to N2 and (Me3Si)2N-NH2 (dilute solution; τ140 deg C1/2 > 1 h) or to HN3 and (Me3Si)2NH (concentrated solution; τ140 deg C1/2 1 h).
