Syntheses and structural characterizations of di-substituted alkylimido hexamolybdates: an insight on bi-alkylimido functionalization.
Bi-alkylimido functionalization of hexamolybdates has been developed and several novel di-substituted alkylimido hexamolybdates with n-butyl, cyclohexyl and tert-butylamines as the imido-releasing reagents have been synthesized in reasonable yields. Their structures have been characterized by elemental analysis, IR, UV-Vis, and ESI mass spectrometry. Moreover, the structures of [Mo(6)O(17)(NCy)(2)](2-) and [Mo(6)O(17)(NCMe(3))(2)](2) have been determined by single-crystal X-ray diffraction techniques. It is notable that the compound (Bu(4)N)(2)[Mo(6)O(17)(NCy)(2)] crystallizes in polar space group Fdd2 with potential ferroelectricity. In addition, theoretical investigation of the reactivity and regioselectivity of bi-alkylimido functionalization has also been conducted. The calculation results show that more energy is required for the bi-functionalization process than for the mono-substitution process, and that the cis-bi-functionalization is the kinetically favored process while trans-[Mo(6)O(17)(NR)(2)](2-) is the thermodynamically favored product.
Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Chunlin
C
Lv
Jin
J
Zhang
Jian
J
Hao
Lei
L
Liu
Yongge
Y
Wei
D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D007536:Isomerism; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D013816:Thermodynamics; D017973:Tungsten Compounds / Q000737:chemistry; D000099294:Polyoxometalates
D056831:Coordination Complexes; D008982:Molybdenum; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates