Addition of Ynamines to the Tungsten η¹-Vinylidene Complexes (η⁵-C₅H₅)(NO)(CO)WCC(H)R

Abstract

With the aim of synthesis of chiral-at-metal complexes with NLO properties, the reaction of ynamines 2a,b with the η1-vinylidene complexes (η1-C5H5)(CO)(NO)WC(H)R (R = C6H5 (1), C(CH3)3 (6), H (8)) was investigated. It has been shown that the substituent R on the η1-vinylidene complex determines the outcome of the reaction. Whereas the reaction of 2a,b with complex 1 gave rise to the expected cyclobutenylidene complexes 4a,b and 5a,b, the reaction of ynamines with complexes 6 yielded the aminocarbene complexes 7a,b and the reaction of η1-vinylidene complexes 8 gave rise to a mixture of compounds 9 and 10. The mechanism of formation of these complexes was investigated. Single-crystal X-ray diffraction data of 4a, 7a, and 9 are reported. Complex 4a is composed of a strong electron-donating and -accepting group conjugated via double bonds of a cyclobutenylidene unit. Hence, the first hyperpolarizability β was determined by hyper-Rayleigh scattering measurements with a stimulating laser beam at λ = 1500 nm. A first hyperpolarizability of β = 105 × 10-30 esu was determined.

Mono(η5-cyclopentadienyl)metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, Electrochemical Studies, and First Hyperpolarizabilities

“…The reference hyperpolarizability β of DR1 in CHCl 3 was measured by comparison of the slopes of I 2w vs concentration plot of the standard in CH 2 Cl 2 and CHCl 3 . Using the hyperpolarizability of DR1 in dichloromethane (β DR1 (CH 2 Cl 2 ) = 70 × 10 –30 esu) the hyperpolarizability of DR1 in CHCl 3 was estimated to be 80 × 10 –30 esu, which is very close to the published value of 74 × 10 –30 esu . Assuming that the scattering contribution from the solvent is negligibly small, this external reference method is used to calculate the β values of complexes according to eq , where s is the slope of the appropriate I 2w vs concentration plot and β ref is the orientational average of the first hyperpolarizability of the reference sample. β = s sample s reference β reference …”

Benzo[c]thiophene Chromophores Linked to Cationic Fe and Ru Derivatives for NLO Materials: Synthesis Characterization and Quadratic Hyperpolarizabilities

“…The reference hyperpolarizability (β) of DR1 in CHCl 3 was measured by comparison of the slopes of I 2w vs. the concentration plot of the standard in CH 2 Cl 2 and CHCl 3 . [44] By using the hyperpolarizability of DR1 in dichloromethane [β DR1 (CH 2 Cl 2 ) = 70ϫ 10 -30 esu], [51] the hyperpolarizability of DR1 in CHCl 3 was estimated to be 80 ϫ 10 -30 esu, which is very close to the published value of 74 ϫ 10 -30 esu. [50] The effect of the refractive indices of the solvents was corrected by using a simple Lorentzian local field.…”

Stable Iso‐osmabenzenes from a Formal [3+3] Cycloaddition Reaction of Metal Vinylidene with Alkynols

“…However, cyclizations of the skeleton of metal vinylidene (MC α C β ) as a unit (see c ) remain scarce. In fact, the reported cyclization is a formal [3+2] cycloaddition reaction 5c. To the best of our knowledge, the [3+3] cyclization reactions of metal vinylidene to construct six‐membered rings have not been reported.…”