IR Spectra and DFT Calculations of ­M–η²‐(NC)–CH₃, CH₃–MNC, and CH₂=M(H)NC Prepared by Reactions of Laser‐Ablated Hf and Ti Atoms with Aceto­nitrile

Abstract

Keywords: Matrix isolation / IR spectroscopy / Hafnium / Titanium / Density functional calculations Laser-ablated Hf and Ti atoms produce M-η 2 -(NC)-CH 3 , CH 3 -MNC, and CH 2 =M(H)NC in reactions with acetonitrile, parallel to the earlier Zr results, based on isotopic substitution and frequencies computed by DFT. These products are the most stable components in the previously proposed reaction path for reactions of metal atoms with acetonitrile, in line with the observed products in other metal systems and DFT calculations. Other plausible products

Boron-Mediated C–C and C≡N Bond Cleavage of Acetonitrile: Matrix Infrared Spectra and Theoretical Calculations

“…The conversion from B-η 2 -(NC)-CH 3 to the more stable CNBCH 3 isomer on the doublet-state surface is mediated by a transition state where the C–C bond is destroyed, which inevitably requires a relatively large energy barrier (63.1 kcal mol –1 ) in the process of full arc photolysis while the side-on complex disappeared. This result is parallel to the previous research that metal insertion complexes were produced similarly via photoisomerization from the initially produced weakly bound complexes with acetonitrile. − Since the reaction was performed under irradiation condition and the energy barrier on the ground state is quite large, we have calculated the excited state of B-η 2 -(NC)-CH 3 for reference. The vertical excitation energy for the lowest-lying electronic transitions is 2.656 eV (466.82 nm), and the transition is able to occur under full arc irradiation (λ > 220 nm).…”

“…Interactions between metal atoms and the electron-rich N moiety have been intensively investigated both experimentally and theoretically. − The nitrogen end of acetonitrile is long known as an effective electron donor, which can easily coordinate to Lewis acids to form various adducts. − It is now well established from a variety of studies that transition-metal atoms easily react with acetonitrile to generate the end-on, side-on, insertion, methylidene, and methylidyne complexes [M←NCCH 3 , M-η 2 -(NC)-CH 3 , CN–M–CH 3 , CN­(H)­MCH 2 , and CN­(H) 2 MCH] in excess argon. − Boron atom reactions with the CN moiety have been studied in a solid argon matrix, and infrared spectra of BNC, BCN, HBCN, and HBNC have been observed in reactions of boron with HCN, and BNCCN, B-η 2 -(NC)-CN, NCBCN, CNBCN, CNBNC, and high-order products have been observed in reactions with cyanogen, as shown in Scheme . Note: only mono boron atom reactions with nitriles and the CN moiety have been studied.…”

Reaction mechanism of hydrogen cyanide catalyzed by gas‐phase titanium

“…On the basis of the performance observed in previous density function theory (DFT) [10] studies of the reaction of transition metals with CH 3 CN and HCN, [1,[5][6][7][8][9] in this article, all stationary points involved in the titled reaction system were optimized using different functions including B3LYP, [11,12] BPW91, [13] M06, [14] and BP86, [15] along with the def2-tzvp/6-31111G(3df, 3pd) basis set. [16,17] Vibration frequency was computed to verify that transition state has only one negative eigenvalue, the energy of other stationary point is a local minimum on the potential energy surfaces (PESs; without any imaginary frequency), simultaneously, the zero-point vibration energy, zero-point correction and a corresponding series of energy were Int J Quantum Chem.…”

“…Over the past decades, the reaction systems of transition metals with the molecules containing nitrile have attracted significant attention, which have been performed experimentally and theoretically because of their own potential economic and environmental value . As the series of reactions of group 4–6 transition metal and actinides (U,Th) with acetonitrile have been reported by Andrew's, and, subsequently, the detailed structure and spin flip reaction mechanism of these systems were investigated by Wang's group . However, the analogous study on hydrogen cyanide is rarely involved.…”

Beryllium Dimer Reactions with Acetonitrile: Formation of Strong Be−Be Bonds

“…Acetonitrile is known as an effective electron donor based on the previous research of reactions with metal atoms [ 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 ], and it could be a good candidate for stabilizing the Be 2 dimer. In this paper, we investigated the reactions of beryllium atoms with acetonitrile by means of matrix-isolation infrared spectroscopy and theoretical calculations, in order to further supplement the reactions of alkali metal with acetonitrile, and search for stable diberyllium complexes that might be formed.…”