Computational and characterization studies of homogeneous and heterogeneous tris(beta-diketonato) complexes with catalytic applications

Abstract

English: Nine [Mn(β-diketonato)3] [β-diketonato = dipivaloymethanato (dpm), 1; acetylacetonato (acac), 2; benzoylacetonato (ba), 3; dibenzoylmethanato (dbm), 4; trifluoroacetylacetonato (tfaa), 5; thenoyltrifluoroacetonato (tfth), 6; trifluorofuroylacetonato (tffu), 7; trifluorobenzoylacetonato (tfba), 8 and hexaflouroacetylacetonato, 9] complexes were synthesized by adapted methods from literature. An attempt was made to graft [Mn(β-diketonato)3] complexes 2-9 onto two dimensional (2-D) Si-wafer supports (S5-S12) via a silane linker. The X-ray photoelectron spectroscopy (XPS) Mn:F atomic ratio results of fluorine containing [Mn(β-diketonato)3] complexes grafted onto amino-functionalized Si-wafer (S9-S12) gave an indicaton that the [Mn(β-diketonato)3] complexes decomposed during the grafting process. Studying Mn2O3 on the hydroxylated Si-wafer surface by the use of XPS, it was confirmed that the Mn 2p photoelectron lines observed for S5-S12 consist mostly of Mn2O3 that has no interaction with the silane linker. Eight [Mn(β-diketonato)3] complexes 1-8 was wet impregnated onto various three dimensional (3-D) solid supports (S12- S28) to form [Mn(β-diketonato)3] model catalysts. Additionally a selection of [M(acac)3] complexes ([Co(acac)3], 12; [Rh(acac)3], 13, and [Ir(acac)3], 14) were grafted onto two dimensional (2-D) Si-wafer supports (S29-S31). While [M(acac)3] complexes ([Cr(acac)3], 10; [Fe(acac)3], 11; [Co(acac)3], 12; [Rh(acac)3], 13, and [Ir(acac)3], 14) were wet impregnated onto various three dimensional (3-D) solid supports (forming S32-S36). The model 2-D and 3-D catalysts were studied and characterized by the means of XPS, TGA and computational chemistry calculations. Selected model 2-D (S5, S7, S8, S12 and S29-S31) and Mn(acac)3 immobilized onto SiO2 (3-D catalysts, S14 as is and heat treated at 100, 130, 250 and 350 °C) were tested for the catalytic self-solvating reaction between ethanol and hexamethylenediisocyanate (HDI) to form hexamethylenediurethane (HDU) to mimic the industrial production of polyurethane. The model 2-D [Mn(β-diketonato)3] (S5, S7, S8 and S12) catalysts showed that as the total group electronegativity, 3(R + R'), increase a general decrease in turnover frequency (TOF) was observed. The model 2-D [M(acac)3] catalysts (S29-S31) showed that with an increase in the metal centre’s Pauling electronegativity a general increase in TOF was observed. The catalytic test on the Mn(acac)3 immobilized onto SiO2 showed that the sample heat treated at 100°C before hand has the highest TOF, which is most probably due to the loss of only one -diketonato ligand making it more active. The chromium(0) Fischer carbene complexes (Cr-FCCs) ([Cr(CO)4(PPh3)=C(OEt)(Fu)], C1; [Cr(CO)5=C(NHCy)(Fu)], C2; [Cr(CO)5=C(NHCy)(Th)], C3 and [Cr(CO)5=C(OEt)(ThTh)], C4) study was in collaboration with the research group of Dr. M Landman at the University of Pretoria. The four Cr(0) FCCs, were obtained and characterized by electrochemistry, XPS and computational chemistry calculations in this study. Penta-carbonyl Cr-FCCs [Cr(CO)5=C(OEt)(Fu)], C5, and [Cr(CO)5=C(OEt)(Th)], C6, were also supplied and anchored onto an amino-functionalized Si-wafer to create an immobilized Cr-FCCs C7 and C8. XPS results showed that the Cr(CO)5=C(OEt)(Fu)], C5, and [Cr(CO)5=C(OEt)(Th)], C6, was successfully anchored onto an amino-functionalized Si-wafer (C7 and C8). The electrochemical study of C1-4 showed that the oxidation potential (Epa) is influenced by the varied substituents on different sites of the Cr-FCCs. The oxidation order of the Cr-FCCs is: [Cr(CO)5=C(OEt)(ThTh)], C4 > [Cr(CO)5=C(NHCy)(Th)], C3 > [Cr(CO)5=C(NHCy)(Fu)], C2 > [Cr(CO)4(PPh3)=C(OEt)(Fu)], C1. The reduction followed the same trend except for the [Cr(CO)4(PPh3)=C(OEt)(Fu)], C1, complex that is reduced at a higher potential than the aminocarbene complexes, [Cr(CO)5=C(OEt)(ThTh)], C4 > [Cr(CO)4(PPh3)=C(OEt)(Fu)], C1 > [Cr(CO)5=C(NHCy)(Th)], C3 > [Cr(CO)5=C(NHCy)(Fu)], C2. The electronic energies of the different conformations obtained by the computational study showed that certain conformations are preferred over others. The computational results were in good agreement with experimental characterization method results. Computational study of HOMO and LUMO orbitals of the Cr- FCCs confirmed that the oxidation process is metal based and the reduction is based across the carbene ligand. The correlation of the oxidation potential (Epa) of the Cr0/Cr+1 redox couple and reduction potential (Epc) of the ligand based reduction with the HOMO energy (EHOMO) and LUMO energy (ELUMO) respectively, showed that with decreasing molecular orbital energy (HOMO and LUMO) an increase to more positive Epa and Epc potentials are obtained.

Afrikaans: Nege [Mn(β-diketonato)3] komplekse (β-diketonato = dpm, 1; asas, 2; ba, 3; dbm, 4; tfaa, 5; tfth, 6; tffu, 7; tfba, 8 en hfaa, 9) is gesintetiseer deur aangepaste metodes verkry uit literatuur. ‘n Poging was aangewend om die [Mn(β-diketonato)3] komplekse 2-9 te bind aan tweedimensionele (2-D) silikonplaatjies (S5-S12) via ‘n silaankoppeling. Die X-straal fotoelektron spektroskopie (XPS) Mn:F atoomverhouding van die fluoor bevattende [Mn(β-diketonato)3] komplekse wat gebind is aan ‘n amino-gefunksionaliseerde silikonplaatjie (S9-S12), het aangedui dat die [Mn(β- diketonato)3] komplekse ontbind het tydens die bindingsproses. Die XPS studie van Mn2O3 op ‘n gehidroksileerde silikonplaatjie het gewys dat die Mn 2p fotoelektronlyne waargeneem vir S5-S12 hoofsaaklik van Mn2O3 is, met geen gepaard gaande interaksie met die silaan nie. Agt [Mn(β- diketonato)3] komplekse 1-8 was deur benattingsimpregnasie geïmmobiliseer op verskeie driedimensionele (3-D) ondersteuningsmateriale (S12-S28). Benewens is die volgende 2-D katalisatore gemaak deur uitgesoekte [M(asas)3] komplekse ([Co(asas)3], 12; [Rh(asas)3], 13, en [Ir(asas)3], 14) te bind aan amino-gefunksionaliseerde silikonplaatjies (S29-S31), sowel as 3-D katalisatore gemaak deur benattingsimpregnasie van [M(asas)3] komplekse ([Cr(asas)3], 10; [Fe(asas)3], 11; [Co(asas)3], 12; [Rh(asas)3], 13, en [Ir(asas)3], 14) op SiO2 (S32-S36). Die model 2-D en 3-D katalisatore is gekarakteriseer met behulp van XPS, termogravimetriese analise (TGA) en kwantum-berekeningschemie. Gekose 2-D (S5, S7, S8, S12 en S29-S31) en Mn(asas)3 geïmmobiliseerd op SiO2 (3-D katalisator, S14 netso sowel as S14 behandeld deur hitte by 100, 130, 250 en 350 °C) se katalitiese aktiwiteit is getoets deur die self-oplossende reaksie tussen etanol en heksametileendiisosianaat (HDI) met heksametileendiuretaan (HDU) (model reaksie vir die industriële produksie van poliuretaan). Die omset frekwensies van die 2-D [Mn(β-diketonato)3] katalisatore (S5, S7, S8 en S12) het ‘n algemene afnemende neiging gewys met die vehoging van die elektronegatiwiteit, 3(R + R'), van die β-diketonato ligande. Die omset frekwensie van die 2-D [M(acac)3] katalisatore (S29-S31) het toegeneem met verhoging in die metaal se Pauling elektronegatiwiteit. Die katalitiese aktiwitets toetsing op die Mn(asas)3 geïmmobiliseerd of SiO2 het gewys dat die monster wat alvorens by ‘n temperatuur van 100 °C behandel is het die hoogste omset frekwensie vertoon. Dit is mees waarskynlik asgevolg van die verlies van een van die -diketonato ligande. Die chroom(0) Fischer karbeen kompleks (Cr-FKK) studie is in samewerking met die navorsingsgroep van Dr. M. Landman van die Universiteit van Pretoria gedoen. Vier Cr-FKKs (Cr-FKK) ([Cr(CO)4(PPh3)=C(OEt)(Fu)], C1; [Cr(CO)5=C(NHCy)(Fu)], C2; [Cr(CO)5=C(NHCy)(Th)], C3 en [Cr(CO)5=C(OEt)(ThTh)], C4) was ontvang en is gekarakteriseer met behulp van elektrochemie, XPS en kwantum-berekeningschemie. Pentakarboniel Cr-FKKs [Cr(CO)5=C(OEt)(Fu)], C5, and [Cr(CO)5=C(OEt)(Th)], C6, verkry vanaf die Universiteit van Pretoria is gebind aan amino-gefunksionaliseerde silikonplaatjies om geïmmobiliseerde Cr-FKKs C7 en C8 te maak. XPS resultate het bewys dat die Cr(CO)5=C(OEt)(Fu)], C5, en [Cr(CO)5=C(OEt)(Th)], C6, suksesvol gebind het op aminoaangepaste silikomplaatjies (C7 and C8). Die elektrochemiese studie van C1-4 met behulp van sikliese voltammetrie het gewys dat die oksidasie potensiaal (Epa) van die Cr0/Cr1+ redokskoppel beïnvloed word deur die varierende substituente op die veskeie bindings omgewings van die Cr-FKKs. Die orde van meer positiewe oksidasie potensiaal van die Cr-FKKs na minder positief is: [Cr(CO)5=C(OEt)(ThTh)], C4 > [Cr(CO)5=C(NHCy)(Th)], C3 > [Cr(CO)5=C(NHCy)(Fu)], C2 > [Cr(CO)4(PPh3)=C(OEt)(Fu)], C1. Die reduksie potensiaal volg dieselfde neiging, behalwe dat die [Cr(CO)4(PPh3)=C(OEt)(Fu)], C1, kompleks gereduseer word by hoër potensiaal vergeleke met die aminokarbeenkomplekse, [Cr(CO)5=C(OEt)(ThTh)], C4 > [Cr(CO)4(PPh3)=C(OEt)(Fu)], C1 > [Cr(CO)5=C(NHCy)(Th)], C3 > [Cr(CO)5=C(NHCy)(Fu)], C2. Die kwantum-berekeningschemie studie het bepaal dat die Cr-FKKs sekere konformasies bo ander konformasies ver kies en die resultate wat verkry is deur die berekeningschemie is in goeie ooreenstemming met die eksperimentele resultate. Die berekende hoogste besette molekuêre orbitale (HBMO) en die laagste onbesette molekulêre orbitale (LOMO) bewys dat die oksidasieproses metaal verband is en die reduksieproses veband is met die reduksie van die ligand tydens die electrochemiese studie van die Cr-FKKs. ‘n Verwantskap tussen die oksidasie potensiaal (Epa) van die Cr0/Cr1+ redokskoppel en die reduksie potensiaal (Epc) van die ligandgebaseerde reduksie, met die HBMO energie (EHBMO) en die LOMO energie (ELOMO) onderskeidelik, toon ‘n verhoging in orbitaal energie ‘n meer positiewe potensiaal tot gevolg het.