Direct Electrochemical Investigations of 17-Electron Complexes of CpM(CO)(3)(*) (M = Mo, W, and Cr)

Photolysis of complexes of the type M(2)(CO)(6)(RC(5)H(4))(2) (where M = W, Mo, Cr and R = H (Cp) or CH(3) (Cp')) leads to the production of short lived 17-electron radicals. Direct electrochemical characterization of these intermediates has been achieved using a technique known as photomodulated voltammetry (PMV). The results from PMV analysis are in excellent agreement with literature estimates for CpMo(CO)(3)(*) and CpCr(CO)(3)(*). However, CpW(CO)(3)(*) is found to be shifted oxidatively 115 mV relative to previous literature estimates. The change in the value for the tungsten complex changes previous estimates to the bond dissociation energy for tungsten metal hydrides by 3.0 +/- 0.9 kcal/mol. Lifetime information on the radicals is also reported based on the phase shift of the electrochemical signal observed by PMV under limiting current conditions.     

Diffractive production of ρ-mesons and of ρπ-systems by neutrinos and antineutrinos on protons

Evidence is presented for diffractive production of -mesons and of -systems invp and chargedcurrent interactions. In the (anti-)neutrino energy range 10 GeVE _v <60 gev=" the=" cross=" sections=" for=" diffractive="> and diffractive production are found to be (0.64±0.14 (stat.)±0.08 (syst.))% and (0.28±0.08 (stat.)±0.04 (syst.))% of the charged-current cross section. The diffractive signal is consistent with being entirely due to diffractivea ₁ production. However, the data cannot distinguish between diffractivea ₁ and diffractive nonresonant production. The experimental distributions ofW, Q ²,x _Bj andy _Bj for diffractive and events are consistent with model predictions.     

Diffractive production of charmed strange mesons by neutrinos and antineutrinos

The diffractive production of charmed strangeD _s ^* and possiblyD _s mesons by neutrinos and antineutrinos on nucleons in hydrogen, deuterium and neon targets is observed. The slope parameter of thet distribution is 3.3±0.8 (GeV)^?2. The production rate per charged current neutrino interaction with an isoscalar target times the D _s ⁺ →φτ⁺ branching fraction is (1.03±0.27)×10^?4.     

Evidence for a NiI active species in the catalytic cross-coupling of alkyl electrophiles

Addition of terpyridine to (TMEDA)Ni(CH3)2 results in the high-yield formation of (terpyridyl)NiMe (3). This NiI organometallic complex was found to be capable of transferring its methyl group to iodocyclohexane to produce methylcyclohexane in high yield. Compound 3 can also serve as an initiator for the catalytic cross-coupling of alkyl electrophiles performed under Negishi-like conditions.     

7-Deazaadenosine: Oligoribonucleotide building block synthesis and autocatalytic hydrolysis of base-modified hammerhead ribozymes

A 7-deazaadenosine ( = tubercidin; c⁷A; 1 ) building block for solid-phase oligoribonucleotide synthesis was prepared. The amino group of 1 was protected with the (dimethylamino)methylidene residue (→ 3 ), and the monomethoxytrityl group was introduced at OH? C(5′) (→ 4 ). Protection of OH? C(2′) was carried out by silylation, showing that use of the (i-Pr)₃Si group resulted in high 2′-O-selectivity (→ 5b , 80%). Reaction of 5b with PCl₃ afforded the phosphonate 7 which was used in solid-phase oligoribonucleotide synthesis. The autocatalytic hydrolysis of hammerhead ribozymes using pG-G-G-A-G-U-C-A-G-U-C-C-C-U-U-C-G-G-G-G-A-C-U-C-U-G-A-A-G-A-G-G-C-G-C as substrate strand (S) and modified G-C-G-C-C-G-A-A-A-C-U-C-C-C as enzyme strand (E) was studied. When c⁷A replaced A¹³ or A¹⁴, a small decrease of catalytic activity was observed, while modification in position A¹⁵ enhanced the autocatalytic hydrolysis. The results demonstrate, that the atom N(7) of adenosine in any of these positions is not crucial for ribozyme action.