Title Kompleksni spojevi molibdena(VI) s asimetričnim karbonohidrazidima Title (english) Molybdenum(VI) complexes with asymmetric carbohydrazides Author Ivana Landripet Mentor Mirta Rubčić (mentor)Committee member Mirta Rubčić (predsjednik povjerenstva)Committee member Josip Požar (član povjerenstva)Committee member Sanda Rončević (član povjerenstva)Committee member Marina Cindrić (član povjerenstva)Granter University of Zagreb Defense date and country 2017-02-28, Croatia Scientific / art field, NATURAL SCIENCES Abstract U okviru ovog rada pripravljena su dva monosupstituirana karbonohidrazida, 1-(2-
hidroksibenziliden)karbonohidrazid, H3Lsal te 1-(piridin-3-ilmetiliden)karbonohidrazid metanol solvat,
H2Lpy·MeOH. Korištenjem tih spojeva kao prekursora pripravljena su dva asimetrično disupstituirana
karbonohidrazida, 1-(2-hidroksi-3-metoksibenziliden)-5-(2-hidroksibenziliden)karbonohidrazid, H4Lovansal,
i 1-(2-hidroksibenziliden)-5-(piridin-3-ilmetiliden)karbonohidrazid, H3Lpy-sal. Pripravljeni asimetrično
disupstituirani derivati H4Lovan-sal i H3Lpy-sal u reakcijama s dioksobis(pentan-2,4-
dionato)molibdenom(VI), [MoO2(acac)2], dali su odgovarajuće kompleksne spojeve molibdena(VI).
Reakcijom H4Lovan-sal s [MoO2(acac)2] u metanolu ili etanolu nastaju dinuklearni kompleksni spojevi tipa
[(MoO2)2Lovan-sal(ROH)2], gdje je Lovan-sal deprotonirani oblik heksadenatnog liganda, dok ROH
označava MeOH ili EtOH. U svim slučajevima radi se o kompleksima u kojima se oba atoma
molibdena nalaze u oktaedarskom okruženju. U slučaju spoja [(MoO2)2(Lovan-sal)(EtOH)2] izolirana su
dva solvata spoja, [(MoO2)2(Lovan-sal)(EtOH)2]·EtOH i [(MoO2)2(Lovan-sal)(EtOH)2] · 2 EtOH. Reakcija
H4Lovan-sal i [MoO2(acac)2] u acetonitrilu rezultirala je polimernim produktom opće formule
[(MoO2)2Lovan-sal]n. Izlaganjem istog parama metanola nastaje kompleksni spoj [(MoO2)2(Lovansal)(
MeOH)2], dok u slučaju etanola nije moguće tim postupkom prirediti analogni spoj.
Reakcijom dioksobis(pentan-2,4-dionato)molibdena(VI) s H3Lpy-sal u metanolu priređen je
mononuklearni kompleks, [MoO2(HLpy-sal)(MeOH)], gdje je HLpy-sal dianionski oblik liganda H3Lpy-sal.
Provođenje analogne sinteze u acetonitrilu rezultira nastankom višenuklearnog spoja [(MoO2)(HLpysal)]
·0,61CH3CN]n. Zagrijavanjem spoja moguće je ukloniti acetonitril, prisutan u kristalnoj rešetki, pri
čemu zaostaje [MoO2(HLpy-sal)]n. Izlaganjem [MoO2(HLpy-sal)]n parama metanola nastaje [MoO2(HLpysal)(
MeOH)].
Svi spojevi su identificirani i okarakterizirani na temelju podataka infracrvene spektroskopije,
difrakcije rentgentskog zračenja na praškastom uzorku, metodama termičke analize, te u slučajevima
kada je to bilo moguće difrakcijom rentgenskog zračenja na jediničnom kristalu.
Abstract (english) Two monosubstituted carbohydrazides, 1-(2-hydroxybenzylidene)carbohydrazide, H3Lsal, and
1-(pyridine-3-ylmethylidene)carbohydrazide methanol solvate, H2Lpy·MeOH, were prepared. Using
such monosubstituted carbohydrazides as pecursors two new asymmetric disubstituted derivatives
were obtained, 1-(2-hydroxy-3-methoxybenzylidene)-5-(2-hydroxybenzylidene)carbohydrazide,
H4Lovan-sal, and 1- (2-hydroxybenzylidene)-5-(pyridin-3-methylidene)carbohydrazids, H3Lpy-sal.
Disubstituted carbohydrazides H4Lovan-sal and H3Lpy-sal in the reactions with dioxobis(pentane-2,4-
dionato)molybdenum(VI), [MoO2(acac)2], yielded dinuclear or polynuclear Mo(VI) complexes.
Reactions of H4Lovan-sal and [MoO2(acac)2] in methanol or ethanol gave dinuclear molybdenum(VI)
complexes of the type [(MoO2)2Lovan-sal(ROH)2], where Lovan-sal denotes deprotonated form of the
hexadenatate ligand used, while ROH stands for MeOH or EtOH. In such complexes both
molybdenum atoms are found in distorted octahedral environment. For the complex [(MoO2)2(Lovansal)(
EtOH)2], two of its solid forms were established, [(MoO2)2(Lovan-sal)(EtOH)2]·EtOH and
[(MoO2)2(Lovan-sal)(EtOH)2] · 2 EtOH. Reaction of H4Lovan-sal and [MoO2(acac)2] in acetonitrile gave
polymeric product [(MoO2)2Lovan-sal]n. By exposing this compound to methanol vapors it was possible to
obtain [(MoO2)2(Lovan-sal)(MeOH)2], whereas the same was not viable in the case of ethanol.
Reaction of H3Lpy-sal and [MoO2(acac)2] in methanol yielded mononuclear complex [MoO2(HLpysal)(
MeOH)], where HLpy-sal stands for dianionic form of the ligand H3Lpy-sal. When the reaction was
conducted in acetonitrile, high-nuclearity complex [(MoO2)(HLpy-sal)]·0,61CH3CN]n was obtained. Upon
heating, acetonitrile molecules can be removed from the lattice, while leaving [MoO2(HLpy-sal)]n. By
exposing this heating residue to methanol vapors it was possible to obtain [MoO2(HLpy-sal)(MeOH)].
All compounds were identified and characterized by means of infrared spectroscopy, X-ray
powder diffraction, thermal analysis and when it was possible via single-crystal X-ray diffraction.
Keywords
dioksobis(pentan-2
4-dionato)molibden(VI)
kompleksni spojevi molibdena (VI)
karbonohidrazidi
otopinska sinteza
rentgentska strukturna analiza
infracrvena spektroskopija
termička analiza
Keywords (english)
dioxobis(pentane-2
4-dionato)molybdenum(VI)
molybdenum(VI) complexes
carbohydrazides
solution synthesis
X-ray diffraction
infrared spectroscopy
X-ray powder diffraction
thermal analysis
Language croatian URN:NBN urn:nbn:hr:217:125563 Study programme Title: Graduate university studies in chemistry; specializations in: Research programme Type of resource Text File origin Born digital Access conditions Open access Terms of use Created on 2017-05-09 12:26:16
