TY - JOUR

T1 - Alumazene adducts with acetonitrile

T2 - Structure and thermal stability

AU - Doinikov, Dmitry A.

AU - Kollhammerova, Iva

AU - Löbl, Jiri

AU - Necas, Marek

AU - Timoshkin, Alexey Y.

AU - Pinkas, Jiri

N1 - Funding Information: This work was supported in Brno by the Ministry of Education, Youth and Sports of the Czech Republic under the project CEITEC 2020 ( LQ1601 ). The X-ray part of the work was carried out with the support of X-ray Diffraction and Bio-SAXS Core Facility of CEITEC. Work in St. Petersburg was supported by SPbSU grant 12.38.255.2014 . Quantum chemical computations were carried out using computational resources provided by Resource Center “Computer Center of SPbU” ( http://cc.spbu.ru ). Funding Information: This work was supported in Brno by the Ministry of Education, Youth and Sports of the Czech Republic under the project CEITEC 2020 (LQ1601). The X-ray part of the work was carried out with the support of X-ray Diffraction and Bio-SAXS Core Facility of CEITEC. Work in St. Petersburg was supported by SPbSU grant 12.38.255.2014. Quantum chemical computations were carried out using computational resources provided by Resource Center “Computer Center of SPbU” (http://cc.spbu.ru). Publisher Copyright: © 2016 Elsevier B.V. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2016/5/1

Y1 - 2016/5/1

N2 - Lewis acid-base adducts of the “inorganic analog of benzene” alumazene [{2,6-(i-Pr)2C6H3NAlMe}3] (1) with acetonitrile (CH3CN, acn) and deuteroacetonitrile (CD3CN, d3-acn) were synthesized, spectroscopically characterized, and their molecular structures were elucidated by the X-ray diffraction analysis as a bis-adduct 1(acn)2 and a tris-adduct 1(d3-acn)3. The thermodynamics of complex formation was investigated experimentally and theoretically. Thermodynamic characteristics of process 1(acn)3·acn (s) = 1(acn)2 (s) + 2 acn (g) in the temperature range 294–370 K have been derived from the vapor pressure–temperature dependence measurements by the static tensimetric method. It is shown that above 435 K in the presence of 1 gaseous acn undergoes irreversible polymerization reaction. Quantum chemical computations at B3LYP/6-311G(d,p) level of theory have been performed for the 1(acn)n and model complexes of [(HAlNH)3] (1m), 1m(acn)n (n = 1–3). Obtained results indicate that for the gas phase adducts upon increasing the number of acn ligands the donor-acceptor Al–N(acn) distances increase in accord with decrease of the donor-acceptor bond dissociation energies.

AB - Lewis acid-base adducts of the “inorganic analog of benzene” alumazene [{2,6-(i-Pr)2C6H3NAlMe}3] (1) with acetonitrile (CH3CN, acn) and deuteroacetonitrile (CD3CN, d3-acn) were synthesized, spectroscopically characterized, and their molecular structures were elucidated by the X-ray diffraction analysis as a bis-adduct 1(acn)2 and a tris-adduct 1(d3-acn)3. The thermodynamics of complex formation was investigated experimentally and theoretically. Thermodynamic characteristics of process 1(acn)3·acn (s) = 1(acn)2 (s) + 2 acn (g) in the temperature range 294–370 K have been derived from the vapor pressure–temperature dependence measurements by the static tensimetric method. It is shown that above 435 K in the presence of 1 gaseous acn undergoes irreversible polymerization reaction. Quantum chemical computations at B3LYP/6-311G(d,p) level of theory have been performed for the 1(acn)n and model complexes of [(HAlNH)3] (1m), 1m(acn)n (n = 1–3). Obtained results indicate that for the gas phase adducts upon increasing the number of acn ligands the donor-acceptor Al–N(acn) distances increase in accord with decrease of the donor-acceptor bond dissociation energies.

KW - Acetonitrile

KW - Alumazene

KW - Computational quantum chemistry

KW - DFT

KW - Polyfunctional Lewis acids

KW - Tensimetric method

UR - http://www.scopus.com/inward/record.url?scp=85044301739&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2016.02.039

DO - 10.1016/j.jorganchem.2016.02.039

M3 - Article

VL - 809

SP - 38

EP - 44

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -