Low-Temperature Isolation of a Labile Silylated Hydrazinium-yl Radical Cation, [(Me Si) N-N(H)SiMe ].

The oxidation of silylated hydrazine, (Me Si) N-N(H)SiMe , with silver salts led to the formation of a highly labile hydrazinium-yl radical cation, [(Me Si) N-N(H)SiMe ] , at very low temperatures (decomposition > -40 °C). EPR, NMR, DFT and Raman studies revealed the formation of a nitrogen-centered radical cation along the N-N unit of the hydrazine. In the presence of the weakly coordinating anion [Al{OCH(CF ) } ] , crystallization and structural characterization in the solid state were achieved.

Intermediates Formed in the Reactions of Organocuprates with α,β-Unsaturated Nitriles.

Conjugate additions of organocuprates are of outstanding importance for organic synthesis. To improve our mechanistic understanding of these reactions, we have used electrospray ionization mass spectrometry for the identification of the ionic intermediates formed upon the treatment of LiCuR2 ⋅LiCN (R=Me, Bu, Ph) with a series of α,β-unsaturated nitriles. Acrylonitrile, the weakest Michael acceptor included, did not afford any detectable intermediates.

Tetraalkylcuprates(III): formation, association, and intrinsic reactivity.

Tetraalkylcuprates are prototypical examples of organocopper(III) species, which remained elusive until their recent detection by NMR spectroscopy. In agreement with the NMR studies, the present electrospray ionization mass spectrometric experiments, as well as supporting electrical conductivity measurements, indicate that LiCuMe(2)·LiCN reacts with a series of alkyl halides RX. The resulting Li(+)Me(2)CuR(CN)(-) intermediates then afford the observable Me(3)CuR(-) tetraalkylcuprate anions upon Me/CN exchanges with added MeLi.

The stability of Cα peptide radicals: why glycyl radical enzymes?

The conformational space of dipeptide models derived from glycine, alanine, phenylalanine, proline, tyrosine, and cysteine has been searched extensively and compared with the corresponding C(α) dipeptide radicals at the G3(MP2)-RAD level of theory. The results indicate that the (least-substituted) glycine dipeptide radical is the thermochemically most stable of these species. Analysis of the structural parameters indicates that this is due to repulsive interactions between the C(α) substituents and peptide units in the radical.

Salts and ionic liquids of resonance stabilized amides.

The synthesis, structure, and bonding of alkali salts of resonance stabilized amides, such as diformylamide (dfa), formylcyanoamide (fca), nitrocyanoamide (nca), and for comparision, the well-known dicyanoamide (dca), are discussed on the basis of experimental and theoretical data. The first structural reports of K(18-crown-6)+dfa-, K(18-crown-6)+fca-, Na+nca-, and Li(TMEDA)+dca- are presented. Examination of the X-ray data reveals almost planar anions with strong cation-anion interactions resulting in network-like structures in the solid state.

Synthesis, structure, and bonding of weakly coordinating anions based on CN adducts.

The addition of alkali or silver salts of dicyanoamide (dca), tricyanomethanide (tcm) and tetracyanoborate (tcb) to a solution of B(C(6)F(5))(3) in diethyl ether affords salts containing very voluminous B(C(6)F(5))(3) adduct anions of the type [E(CN)(n)(-)] x [B(C(6)F(5))(3)](n): E = N (dca_nb with n = 1, 2; b = B(C(6)F(5))(3)); E = C (tcm_nb with n = 1, 2, 3), and E = B (tcb_nb with n = 1, 2, 3, 4). Salts bearing these anions such as B[(CN) x B(C(6)F(5))(3)](4)(-) (= [B(CN)(4)(-)] x [B(C(6)F(5))(3)](4)), C[(CN) x B(C(6)F(5))(3)](3)(-) (= [C(CN)(3)(-)] x [B(C(6)F(5))(3)](3)), and N[(CN) x B(C(6)F(5))(3)](2)(-) (=[N(CN)(2)(-)] x [B(C(6)F(5))(3)](2)) can be prepared in good yields. They are thermally stable up to over 200 degrees C and dissolve in polar organic solvents.

Synthesis and structure of monomeric, trimeric, and mixed phenylcyanamides.

In a new synthetic approach phenylcyanamide (Hpca) was synthesized by methylation of phenylthiourea followed by a basic work-up. All products along the synthetic route have been fully characterized by means of NMR, IR, and X-ray studies. The first structural report of neutral mixed crystals of phenylcyanamide containing monomeric and trimeric Hpca is presented.

Blue alkali dinitrosomethanides: synthesis, structure, and bonding.

Explosive alkali dinitrosomethanides (M[HC(NO)2]; M = Li, Na, K, Cs) were prepared in a new, simple, high-yielding synthetic procedure, fully characterized, and shown to be stable at ambient temperature. Alkali dinitrosomethanides are of widespread interest to pharmaceutical and materials scientists alike.