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• 4346-59-2 para-methoxyphenyldiazonium chloride 
• 36579-71-2 naphtho[1,8-cd]1,2-diselenole 

Relevant academic research and scientific papers

Successive Change in Conformation Caused by p-Y Groups in 1-(MeSe)-8-(p-YC6H4Se)C10H6: Role of Linear Se...Se-C Three-Center-Four-Electron versus n(Se)...n(Se) Two-Center-Four-Electron Nonbonded Interactions

The structure of 1-(methylselanyl)-8-(p-anisylselanyl)naphthalene (2) and 1-(methylselanyl)-8-(p-chlorophen-ylselanyl)naphthalene (3) was studied by X-ray crystallographic analysis. The structures around the Se-Me and Se-C6H4OMe-p (Se-CAn) groups in 2 are close to type A and type B, respectively: type A if the Se-C bond is almost perpendicular to the naphthyl plane and type B when the Se-C bond is placed on the plane. Those around the Se-Me and Se-C6H4Cl-p (Se-CAr) groups in 3 are type B and type A, respectively. The nonbonded Se...Se distances of 2 and 3 are 3.0951(8) and 3.1239(7) A, respectively. The structure of 3 is very different from that observed in 1-(methylselanyl)-8-(phenylselanyl)naphthalene (1), the structure of which is type C, where the two Se-C bonds decline by about 45° from the naphthyl plane. The structure of 3 strongly suggests the contribution of the nonbonded n(SeAr)...σ*(Se-CMe) three-center - four-electron (3c-4e) type interaction. The nonbonded n(SeMe)...σ*(Se-CAn) 3c-4e type interaction must partly contribute to the structure of 2. To clarify the nature of the n(Se)...σ*(Se-C) 3c-4e type interaction observed in 2 and 3, together with the n type two-center - four-electron interaction in 1, ab initio MO calculations with the B3LYP/6-311++G(3df,2pd) method were performed on model a, HaHbSe...SeHa′Hb′, where the naphthylidene group was replaced by Ha and Ha′ and the Me and Ar groups by Hb and Hb′. Two structures are optimized to be energy minima with b = b′ = ca. 74° and 155°. The latter corresponds to the conformation observed in 1, which is controlled by HOMO (π*(Se...Se)); the former is HOMO-1 (σ(Se...Se))-controlled. On the contrary, similar calculations with the B3LYP/6-311+G(2d,p) method on naphthalene-1,8-diselenol show that the type A - type B pairing is evaluated to be most stable, which explains the conformations observed in 2 and 3: the n(Se)...σ*(Se-C) 3c-4e interaction, as well as π-orbitals of the naphthyl group, play an important role in the pairing. The resonance effect of OMe and the inductive effect of Cl must also be important to determine the structures of 2 and 3, respectively. The character of CT calculated by the natural population analysis for the diselenol supports further the n(Se)...σ*(Se-C) 3c-4e interaction.

Novel Substituent Effect on 77Se NMR Chemical Shifts Caused by 4c-6e versus 2c-4e and 3c-4e in Naphthalene Peri Positions: Spectroscopic and Theoretical Study

δ(8Se) values for 1-[8-(P-YC6H4Se)C10H6]SeSe[C 10H6(SeC6H4Y-p)-8′]-1′ (1: Y = H, OMe, Me, Cl, Br, COOEt, and NO2) showed a good correlation with those of 1-(MeSe)-8-(p-YC6H4Se)C10H6 (2). While the δ(1Se) values correlated well with δ(8Se) in 2 with a positive proportionality constant of 0.252 (regular correlation), a similar correlation for 1 gave a negative proportionality constant of -0.282 (inverse correlation). To clarify the mechanism associated with the inverse correlation in 1, together with the regular correlation in 2, ab initio MO calculations, containing the GIAO magnetic shielding tensor for the Se nucleus (σ(Se)), were performed on p-YC6H4ASeH- - -BSeH-BSeH- - -HASeC6H4Y-p (3: model of Se4 4c-6e for 1) and on p-YC6H4ASeH- - -BSeH2 (4 and 5: models of Se2 π type 2c-4e and ASe- - -BSe-H 3c-4e for 2, respectively) with the 6-311+G(2d,p) basis sets at B3LYP and/or HF levels. The characteristic nature of the substituent effects on atomic charges and δ(Se) values in 3 is demonstrated to be Yδ-←C6H4-Seδ+- - -Seδ+-Seδ+- - -Seδ+-C6H4-Yδ- and Yδ-←C6H4-Sedown- - -Seup-Seup- - -Sedown-C6H4-Yδ-, respectively, (Y = electron-withdrawing) and in 5 is Yδ-←C6H4-Seδ+- - -Seδ--Hδ+ and Yδ-←C6H4-Sedown- - -Sedown-Hdown, respectively. In the case of 4, a substantial contribution through the naphthylidene group is suggested. These results indicate that the nature of the interaction between the linear four Se atoms in 1 is of the 4c-6e type and that between the two Se atoms in 2 is π type 2c-4e and/or 3c-4e according to the conformations around the Se atoms. The observed NMR parameters are well explained by model calculations on 3-5. Plots of 4J(1Se,8Se) versus δ(8Se) of 1 and 2 gave good correlations with negative proportionality constants, which indicates that the J values become larger as the electron density on the 8Se atoms increases.