TY - JOUR
T1 - Reactivity of Transition Metal Gallylene Complexes Toward Substrates with Multiple Carbon-Element Bonds
AU - Dodonov, Vladimir A.
AU - Sokolov, Vladimir G.
AU - Baranov, Evgeny V.
AU - Skatova, Alexandra A.
AU - Xu, Wenhua
AU - Zhao, Yanxia
AU - Yang, Xiao Juan
AU - Fedushkin, Igor L.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/9/26
Y1 - 2022/9/26
N2 - Reactivity of transition metal complexes containing the redox-active gallylene (dpp-bian)Ga ligand (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward isocyanide, isocyanate, isothiocyanate, and ketene substrates is described. The reaction of [(dpp-bian)GaCr(CO)5] (1) with tBuNC results in a dative complex [(dpp-bian)Ga(CNtBu)Cr(CO)5] (2), while compound [(dpp-bian)GaCr(CO)5]2[Na(THF)2]2(3) reacts with tBuNC to give the coordination polymer [(dpp-bian)GaCr(CO)5][Na(CNtBu)(THF)]n(5). Treatment of [(dpp-bian)GaCr(CO)5]2[Na(THF)2]2with an excess of PhNCO results in trimerization of the latter and formation of complex [(dpp-bian)GaCr(CO)5][Na(PhNCO)3(Et2O) (DME)] (4). [(dpp-bian)GaFeCp(CO)2] (7) treated with Ph2CCO or PhNCS results in cycloaddition products [(dpp-bian)(Ph2CCO)GaFeCp(CO)2] (8) and [(dpp-bian)(PhNCS)GaFeCp(CO)2] (9). The formation of 2 and 9 was found to be reversible, which offers a means for facile regulation of transition metal center reactivity and cooperative substrate activation. New compounds were characterized by EPR (2), NMR (4, 8, and 9), and IR spectroscopy (2, 4, 5, 8, and 9). The molecular structures of 2, 4, 5, 8, and 9 were established by single-crystal X-ray diffraction analysis. Electronic structures of the compounds have been examined by DFT calculations.
AB - Reactivity of transition metal complexes containing the redox-active gallylene (dpp-bian)Ga ligand (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward isocyanide, isocyanate, isothiocyanate, and ketene substrates is described. The reaction of [(dpp-bian)GaCr(CO)5] (1) with tBuNC results in a dative complex [(dpp-bian)Ga(CNtBu)Cr(CO)5] (2), while compound [(dpp-bian)GaCr(CO)5]2[Na(THF)2]2(3) reacts with tBuNC to give the coordination polymer [(dpp-bian)GaCr(CO)5][Na(CNtBu)(THF)]n(5). Treatment of [(dpp-bian)GaCr(CO)5]2[Na(THF)2]2with an excess of PhNCO results in trimerization of the latter and formation of complex [(dpp-bian)GaCr(CO)5][Na(PhNCO)3(Et2O) (DME)] (4). [(dpp-bian)GaFeCp(CO)2] (7) treated with Ph2CCO or PhNCS results in cycloaddition products [(dpp-bian)(Ph2CCO)GaFeCp(CO)2] (8) and [(dpp-bian)(PhNCS)GaFeCp(CO)2] (9). The formation of 2 and 9 was found to be reversible, which offers a means for facile regulation of transition metal center reactivity and cooperative substrate activation. New compounds were characterized by EPR (2), NMR (4, 8, and 9), and IR spectroscopy (2, 4, 5, 8, and 9). The molecular structures of 2, 4, 5, 8, and 9 were established by single-crystal X-ray diffraction analysis. Electronic structures of the compounds have been examined by DFT calculations.
UR - http://www.scopus.com/inward/record.url?scp=85138764974&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.2c01296
DO - 10.1021/acs.inorgchem.2c01296
M3 - Article
C2 - 36102598
AN - SCOPUS:85138764974
SN - 0020-1669
VL - 61
SP - 14962
EP - 14972
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 38
ER -