RESUMEN
Augmented reality (AR) has the capacity to afford a virtual experience that obviates the reliance on using two-dimensional representations of 3D molecules for teaching stereochemistry to undergraduate students. Using a combination of quantitative instruments and qualitative surveys/interviews, this study explored the relationships between students' attitudes, perceived cognitive load, spatial ability, and academic performance when engaging in an asynchronous online stereochemistry activity. Our activity was designed using elements of game-based learning, and integrated AR technologies. The control group was provided with a copy of our activity that used two-dimensional drawings, whereas the AR group completed an activity using the AR technologies. For this cohort of students, results indicated significant improvement in academic performance in both the control and AR groups. The introduction of AR technologies did not result in the AR group outperforming the control group. Participants from both groups displayed significant improvements in spatial ability throughout the research period. Further, a moderate correlation (r s = 0.416) between students' spatial ability and academic performance was found. No significant intergroup differences in the perceived cognitive loads of students were observed. A significant difference was observed on one item of the Intellectual Accessibility subscale of the ASCI (V2), Complicated-Simple. We found no correlation for student attitude or cognitive load with academic performance. The findings of this study provide insights for future AR-related studies to explore the role of spatial ability, student attitude, and cognitive load in learning performance. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s10956-022-09957-0.
RESUMEN
The chemistry foundation year at the University of East Anglia is a diverse cohort with a wide range of prior educational experience and confidence levels. A flexible learning program combining extensive online materials intended for asynchronous study and face to face peer instruction is provided. Study is divided into weekly topics. Students are directed to take a short introductory quiz at the beginning of the week, feedback on which allows them to tailor the extent of asynchronous learning to their own needs. All students attend a highly interactive synchronous teaching session which utilises active learning to develop their conceptual understanding. The week concludes with a reflective formative test. Measures of student activity on the online platform and audience response technology in the lecture theatre provide a quantitative picture of engagement with tailored blended learning, while semi-structured interviews provide qualitative insight into the student perception.
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A new family of cyclometallated gold(III) thiolato complexes based on pyrazine-centred pincer ligands has been prepared, (C^Npz ^C)AuSR, where C^Npz ^C=2,6-bis(4-But C6 H4 )pyrazine dianion and R=Ph (1), C6 H4 tBu-4 (2), 2-pyridyl (3), 1-naphthyl (1-Np, 4), 2-Np (5), quinolinyl (Quin, 6), 4-methylcoumarinyl (Coum, 7) and 1-adamantyl (8). The complexes were isolated as yellow to red solids in high yields using mild synthetic conditions. The single-crystal X-ray structures revealed that the colour of the deep-red solids is associated with the formation of a particular type of short (3.2-3.3â Å) intermolecular pyrazineâ â â pyrazine π-interactions. In some cases, yellow and red crystal polymorphs were formed; only the latter were emissive at room temperature. Combined NMR and UV/Vis techniques showed that the supramolecular π-stacking interactions persist in solution and give rise to intense deep-red photoluminescence. Monomeric molecules show vibronically structured green emissions at low temperature, assigned to ligand-based 3 IL(C^N^C) triplet emissions. By contrast, the unstructured red emissions correlate mainly with a 3 LLCT(SRâ{(C^Npz ^C)2 }) charge transfer transition from the thiolate ligand to the πâ â â π dimerized pyrazine. Unusually, the π-interactions can be influenced by sample treatment in solution, such that the emissions can switch reversibly from red to green. To our knowledge this is the first report of aggregation-enhanced emission in gold(III) chemistry.
RESUMEN
Treatment of Me(2)S·B(C(6)F(5))(n) H(3-n) (n=1 or 2) with ammonia yields the corresponding adducts. H(3)N·B(C(6)F(5))H(2) dimerises in the solid state through N-H···H-B dihydrogen interactions. The adducts can be deprotonated to give lithium amidoboranes Li[NH(2)B(C(6)F(5))(n)H(3-n)]. Reaction of the n=2 reagent with [Cp(2)ZrCl(2)] leads to disubstitution, but [Cp(2)Zr{NH(2)B(C(6)F(5))(2)H}(2)] is in equilibrium with the product of ß-hydride elimination [Cp(2)Zr(H){NH(2)B(C(6)F(5))(2)H}], which proves to be the major isolated solid. The analogous reaction with [Cp(2)HfCl(2)] gives a mixture of [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)] and the N-H activation product [Cp(2)Hf{NHB(C(6)F(5 )(2)H}]. [Cp(2)Zr{NH(2)B(C(6)F(5))(2)H}(2)]·PhMe and [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)]·4(thf) exhibit ß-B-agostic chelate bonding of one of the two amidoborane ligands in the solid state. The agostic hydride is invariably coordinated to the outside of the metallocene wedge. Exceptionally, [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)]â PhMe has a structure in which the two amidoborane ligands adopt an intermediate coordination mode, in which neither is definitively agostic. [Cp(2)Hf{NHB(C(6)F(5))(2)H}] has a formally dianionic imidoborane ligand chelating through an agostic interaction, but the bond-length distribution suggests a contribution from a zwitterionic amidoborane resonance structure. Treatment of the zwitterions [Cp(2)MMe(µ-Me)B(C(6)F(5))(3)] (M=Zr, Hf) with Li[NH(2)B(C(6)F(5))(n)H(3-n)] (n=2) results in [Cp(2) MMe{NH(2)B(C(6)F(5))(2)H}] complexes, for which the spectroscopic data, particularly (1)J(B,H), again suggest ß-B-agostic interactions. The reactions proceed similarly for the structurally encumbered [Cp''(2)ZrMe(µ-Me)B(C(6)F(5))(3)] precursor (Cp''=1,3-C(5)H(3)(SiMe(3))(2) , n=1 or 2) to give [Cp''(2)ZrMe{NH(2)B(C(6)F(5))(n)H(3-n)}], both of which have been structurally characterised and show chelating, agostic amidoborane coordination. In contrast, the analogous hafnium chemistry leads to the recovery of [Cp''(2)HfMe(2)] and the formation of Li[HB(C(6)F(5))(3)] through hydride abstraction.
RESUMEN
The phosphinoborane adduct H(3)P x B(C(6)F(5))(3) can be deprotonated using LiN(SiMe(3))(2) to give the phosphidoborate salt Li[H(2)PB(C(6)F(5))(3)], which was converted to the phosphidodiborates Li[H(2)P{B(C(6)F(5))(3)}(2)] and Li[H(2)P{B(C(6)F(5))(3)}{BH(3)}] by treatment with an equivalent of B(C(6)F(5))(3) or Me(2)S.BH(3), respectively. A series of anions of the form [RR'P{M(C(6)F(5))(3)}{BH(3)}](-), where R = R' = Ph or R= (t)Bu, R' = H, and M = B or Al, were prepared (through treatment of salts Li[RR'P(BH(3))] with the corresponding Lewis acid) and characterized using multinuclear NMR, elemental analysis and X-ray crystallography. The solid state structures of [Li(Et(2)O)(x)][Ph(2)P{M(C(6)F(5))(3)}{BH(3)}] exhibit eta(2)-bonding of the BH(3) group to the cationic lithium center. The attempted preparation of an analogous series with amide cores of the form [R(2)N{B(C(6)F(5))(3)}{BH(3)}](-) proved unsuccessful; among the competing reaction pathways hydride abstraction occurred preferentially to yield Li[HB(C(6)F(5))(3)] and dimers or higher oligomers with the composition (R(2)NBH(2))(n).
Asunto(s)
Amidas/química , Amidas/síntesis química , Boranos/química , Hidrocarburos Fluorados/química , Compuestos Organometálicos/química , Fosfinas/química , Aniones/química , Cristalografía por Rayos X , Modelos Moleculares , Conformación Molecular , Estructura Molecular , EstereoisomerismoRESUMEN
The mono(salicylaldiminato) complexes Ti{3-tBu-2-(O)C6H3CH=N(R)}Cl3(THF)(where R = C6H5, C6F5) react with the metallated pyrrolylaldiminato ligand, K[2-(C6H5NCH)C4H3N], to afford the first examples of hybrid salicylaldiminato-ligated octahedral titanium complexes; the pre-catalysts give from very high to extremely high ethene polymerisation productivities when activated with MAO.
RESUMEN
Facile deprotonation of H3N.B(C6F5)3 with [M(NMe2)4](M = Zr or Ti) yields the novel amidoborate complexes [Zr(NMe2)3{NH2B(C6F5)3}(HNMe2)] and [Ti(NMe2)3{NH2B(C6F5)3}].
RESUMEN
The reactions between the cyclic sec. amines pyrrolidine and piperidine with B(C6F5)3 yield Lewis acid-base adducts with both intra- and inter-molecular hydrogen bonding interactions between C-H and N-H groups and aryl-fluorines in the solid state.
RESUMEN
Reaction of Zn(C6F5)2·toluene (two equivalents) with 1,3-dipropoxy-p-tert-butyl-calix[4]arene (L(1)H2) led to the isolation of the complex [{Zn(C6F5)}2L(1)] (1), whilst similar use of Zn(Me)2 resulted in the known complex [{Zn(Me)}2L(1)] (2). Treatment of L(1)H2 with in situ prepared Zn{N(SiMe3)2}2 in refluxing toluene led to the isolation of the compound [(Na)ZnN(SiMe3)2L(1)] (3). The stepwise reaction of L(1)H2 and sodium hydride, followed by ZnCl2 and finally NaN(SiMe3)2 yielded the compound [Zn{N(SiMe3)2}2L(1)] (4). The reaction between three equivalents of Zn(C6F5)2·toluene and oxacalix[3]arene (L(2)H3) at room temperature formed the compound {[Zn(C6F5)]3L(2)} (5); heating of 5 in acetonitrile caused the ring opening of the parent oxacalix[3]arene and rearrangement to afford the complex [(L(2))Zn6(C6F5)(R)(RH)OH]·5MeCN R = C6F5CH2-(p-(t)BuPhenolate-CH2OCH2-)2-p-(t)BuPhenolate-CH2O(-))(3-) (6). The molecular structures of the new complexes 1, 3 and 6, together with that of the known complex 2, whose solid state structure has not previously been reported, have been determined. Compounds 1, 3-5 have been screened for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide. Compounds featuring a Zn-C6F5 fragment were found to be poor ROP pre-catalysts as they did not react with benzyl alcohol to form an alkoxide. By contrast, compound 4, which contains a zinc silylamide linkage, was the most active of the zinc-based calix[4]arene compounds screened and was capable of ROP at ambient temperature with 65% conversion over 4 h.
RESUMEN
Treatment of TiCl(NMe(2))(3) with H(3)N·B(C(6)F(5))(3) results in N-H activation and ligand exchange to yield the structurally characterised salt [TiCl(NMe(2))(2)(NMe(2)H)(2)](+)[Ti[triple bond]NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-). Cation exchange with [Me(4)N]Cl, [Ph(4)P]Cl and [(PhCH(2))Ph(3)P]Cl yields the respective ammonium and phosphonium salts of the [Ti[triple bond]NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-) anion. X-ray crystallography reveals that the essential trigonal bipyramidal geometry and composition of the anion is retained in each of these salts despite some minor variations in the Ti-N-B angle and the nature of the interionic interactions. Electronic investigation by DFT calculations confirmed the Ti-N triple bond character implied by the experimentally determined bond length, with the HOMO and HOMO-1 having Ti-N π-bonding character. The dimethylamine ligands of the anion resist substitution by moderate bases but can be displaced by pyridine to give a pentacoordinate anion. In contrast, addition of 2,2'-bipyridyl gives a neutral octahedral complex. Treatment of the pyridine complex with TlCp results in the formation of a four coordinate anionic cyclopentadienyl complex.
RESUMEN
Treatment of the tris(pyrazolyl)borate metal triamides Tp'M(NMe(2))(3), where Tp' = (C(3)H(3)N(2))(3)BH (Tp) or (3,5-Me(2)C(3)HN(2))(3)BH (Tp*) and M = Ti, Zr and Hf, with the Brønsted acidic Lewis adduct (C(6)F(5))(3)B·NH(3) in toluene solution leads to the formation of Tp'M(NMe(2))(2){NH(2)B(C(6)F(5))(3)} complexes. The exception to this was the attempted preparation of Tp*Ti(NMe(2))(2){NH(2)B(C(6)F(5))(3)} which was unsuccessful. Where Tp' = Tp and M = Ti and Zr and where Tp' = Tp* and M = Zr the complexes have been characterized by single crystal X-ray diffraction methods, revealing the first examples of octahedral amidoborane complexes of the group 4 metals. Attempts to drive the reactions to completion resulted in competing preferential hydrolysis of the amidoborane group, regenerating (C(6)F(5))(3)B·NH(3).
RESUMEN
Compounds of the new tetrafluorophthalimido anion, [C(6)F(4)(CO)(2)N](-), are readily accessible by treatment of tetrafluorophthalimide with either LiNPr(i)(2) or mixtures of NEt(3) and Me(3)ECl (E = Si or Sn), to give C(6)F(4)(CO)(2)N-X (X = Li 3, SiMe(3)4, and SnMe(3)5). The reaction of the trimethylsilyl derivative 4 with AgF leads cleanly to the ion pair complex [Ag(NCMe)(2)][Ag(N(CO)(2)C(6)F(4))(2)] (6·2MeCN), which contains a linear [Ag{N(CO)(2)C(6)F(4)}(2)](-) anion and a tetracoordinate Ag(+) cation. Compound 6 reacts with iodine to give the N-iodo compound C(6)F(4)(CO)(2)NI 7, which crystallises as an acetonitrile adduct. Treatment of 6 with LAuCl affords LAu{N(CO)(2)C(6)F(4)} (L = Ph(3)P 8a, Cy(3)P 8b, or THT 9), whereas the reaction with AuCl in acetonitrile affords the heterobinuclear compound [Ag(MeCN)(2)][Au{N(CO)(2)C(6)F(4)}(2)]·MeCN (10·3MeCN). The tetrafluorophthalimido ligand is not readily displaced by donor ligands; however, the addition of B(C(6)F(5))(3)(Et(2)O) to a diethyl ether solution of 8a leads to the salt [Au(PPh(3))(2)][N{COB(C(6)F(5))(3)}(2)C(6)F(4))] 11. The analogous reaction of (THT)Au{N(CO)(2)C(6)F(4)} with B(C(6)F(5))(3) in toluene in the presence of excess norbornene (nb) gives [Au(nb)(3)][N{COB(C(6)F(5))(3)}(2)C(6)F(4))] 12. Compounds 11 and 12 contain a new non-coordinating phthalimido-bridged diborate anion with O-bonded boron atoms. The crystal structures of compounds 2-11 are reported.
RESUMEN
Treatment of Cp(2)HfCl(2) with two equivalents of LiNH(2)BH(C(6)F(5))(2) in toluene solution yields Cp(2)Hf{NHBH(C(6)F(5))(2)}, which has been crystallographically characterised. The otherwise base-free [NHBH(C(6)F(5))(2)] complex is stabilised by an agostic interaction.
RESUMEN
The Grignard reagent Ar(F)'MgBr (Ar(F)' = 4-(C(6)F(5))C(6)F(4)) reacts with Me(3)SiCl, Me(2)SiCl(2) and Me(3)SnCl to give the 4-nonafluorobiphenyl group 14 complexes Ar(F)'Me(3)Si, (Ar(F)')(2)Me(2)Si and Ar(F)'Me(3)Sn respectively. Ar(F)'Me(3)Sn undergoes only methyl group exchange when treated with BBr(3), yielding Ar(F)'Me(2)SnBr. The solid state structures of Ar(F)'Me(3)Sn and Ar(F)'Me(2)SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of Ar(F)'MgBr and BF(3) was not selective, while one equivalent of Ar(F)'MgBr and (Ar(F))(2)BF (Ar(F) = C(6)F(5)) reacted cleanly to give (Ar(F))(2)Ar(F)'B. Treatment of BCl(3) with three equivalents of Ar(F)'Li, prepared at low temperature from the reaction between Ar(F)'Br and n-BuLi, yielded (Ar(F)')(3)B. The molecular structures of the acetonitrile adducts of (Ar(F))(2)Ar(F)'B and (Ar(F)')(3)B closely resemble that of (Ar(F))(3)B.NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (Ar(F)')(2)BOH.OH(2) as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl(2) in diethyl ether giving first [(Ar(F)')Zn(micro-Cl)(OEt(2))](2) then (Ar(F)')(2)Zn(OEt(2))(2), both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl(2) requires the use of tetrahydrofuran as the solvent and yields (Ar(F)')(2)Hg(THF)(2).
RESUMEN
The crystalline ion-pair [TiCl(NMe(2))(2)(NMe(2)H)(2)](+)[TiCl(2){NB(C(6)F(5))(3)}(NMe(2)H)(2)](-), in which the anion has a triply bonded nitridoborate ligand, is formed through the multiple activation of H(3)N x B(C(6)F(5))(3) when treated with [Ti(NMe(2))(3)Cl].
RESUMEN
The ammonia adduct of tris(pentafluorophenyl)boron, (C6F5)3B.NH3, is a potentially tri-functional hydrogen-bond donor. Co-crystallisation with the bases acetonitrile, pyridine, tetrahydrofuran, tetramethylethylenediamine, 15-crown-5, 1,4-diazabicyclo[2.2.2]octane (DABCO), pyrazine and 4,4'-bipyridine results, not in donor exchange, but in the formation of supermolecules assembled through hydrogen bonding to second coordination sphere acceptors. The complexes have been characterised by elemental analysis, multinuclear NMR and single-crystal diffraction methods. The solid-state architectures range in complexity, from the hydrogen bonded pairing of (C6F5)3B.NH3, with a single monodentate acceptor molecule (e.g. MeCN to form (C6F5)3B.NH3.NCMe), through complexation with all three N-H groups to the macrocycle 15-crown-5, to the formation of infinite one-dimensional chains with pyrazine and DABCO, and to two-dimensional networks with the divergent acceptor 4,4'-bipyridine.
RESUMEN
The title ionic solid, [Ti(C(2)H(6)N)3(C(2)H(7)N)2][Ti(C(18)BF(15)N)(C(18)H(2)BF(15)N)Cl(C(2)H(7)N)(2)].C(7)H(8), (I), comprises a cation with three dimethylamide ligands in the equatorial plane and two dimethylamine ligands positioned axially in a trigonal-bipyramidal geometry about the central Ti(IV) atom. The anion has a highly distorted octahedral structure. The two dimethylamine ligands are coordinated mutually trans. The chloride is trans to the tris(pentafluorophenyl)boron-amide, while the sixth coordination site is occupied by an ortho-F atom of the tris(pentafluorophenyl)boron-amide group in a trans disposition with respect to the tris(pentafluorophenyl)boron-nitride ligand. The most significant feature of the anion is the presence of an unprecedented terminal Ti[triple-bond]N moiety [1.665 (2) A], stabilized by coordination to B(C(6)F(5))(3), with a Ti[triple-bond]N-B angle of 169.50 (19) degrees.
Asunto(s)
Compuestos Organometálicos/química , Titanio/química , Aniones/química , Modelos Moleculares , Conformación Molecular , Tolueno/químicaRESUMEN
Treatment of the homoleptic titanium amides [Ti(NR(2))(4)] (R=Me or Et) with the Brønsted acidic reagent H(3)NB(C(6)F(5))(3) results in the elimination of one molecule of amine and the formation of the four-coordinate amidoborate complexes [Ti(NR(2))(3){NH(2)B(C(6)F(5))(3)}], the identity of which was confirmed by X-ray crystallography. The reaction with [Zr(NMe(2))(4)] proceeds similarly but with retention of the amine ligand to give the trigonal-bipyramidal complex [Zr(NMe(2))(3){NH(2)B(C(6)F(5))(3)}(NMe(2)H)]. Cyclopentadienyl (Cp) amidoborate complexes, [MCp(NR(2))(2){NH(2)B(C(6)F(5))(3)}] (M=Ti, R=Me or Et; M=Zr, R=Me) can be prepared from [MCp(NR(2))(3)] and H(3)NB(C(6)F(5))(3), and exhibit greater thermal stability than the cyclopentadienyl-free compounds. H(3)NB(C(6)F(5))(3) reacts with nBuLi or LiN(SiMe(3))(2) to give LiNH(2)B(C(6)F(5))(3), which complexes with strong Lewis acids to form ion pairs that contain weakly coordinating anions. The attempted synthesis of metallocene amidoborate complexes from dialkyl or diamide precursors and H(3)NB(C(6)F(5))(3) was unsuccessful. However, LiNH(2)B(C(6)F(5))(3) does react with the highly electrophilic reagents [MCp(2)Me(mu-Me)B(C(6)F(5))(3)] to give [MCp(2)Me(mu-NH(2))B(C(6)F(5))(3)] (M=Zr or Hf). Comparison of the molecular structures of the Group 4 amidoborate complexes reveals very similar B--N, Ti--N and Zr--N bond lengths, which are consistent with a description of the bonding as a dative interaction between an {M(L)(n)(NH(2))} fragment and the Lewis acid B(C(6)F(5))(3). Each of the structures has an intramolecular hydrogen-bonding arrangement in which one of the nitrogen-bonded hydrogen atoms participates in a bifurcated FHF interaction to ortho-F atoms.
Asunto(s)
Amidas/química , Compuestos de Boro/química , Compuestos Organometálicos/química , Elementos de Transición/química , Cristalografía por Rayos X , Modelos Moleculares , Estructura Molecular , Compuestos Organometálicos/síntesis química , EstereoisomerismoRESUMEN
The successive addition of KCN and Ph3CCl to B(C6F4-C6F5-2)3 (PBB) affords triphenylmethyl salts of the [NC-PBB]- anion. By contrast, the analogous reaction with sodium dicyanamide followed by treatment with Ph(3)CCl leads to the zwitterionic aminoborane H2NB(C12F9)2C12F8, via nucleophilic attack on an o-F atom, together with CPh3[F-PBB]. Whereas treatment of [NC-PBB]- with either PBB or B(C6F5)3 fails to give isolable cyano-bridged diborates, the reaction of Me3SiNC-B(C6F5)3 with PBB in the presence of Ph3CCl affords [Ph3C][PBB-NC-B(C6F5)3]. Due to steric hindrance this anion is prone to borane dissociation. The longer linking group N(CN)2- gives the very voluminous anions [N[CNB(C6F5)3]2]- and [N(CN-PBB)2]-. A comparison of propylene polymerisations with rac-Me2Si(Ind)2ZrMe2 activated with the various boranes or trityl borates gives an anion-dependent activity sequence, in the order [NC-PBB]- < [MeB(C6F5)3]- < [MePBB]- approximately [PBB-NCB(C6F5)3]- approximately [N[CNB(C6F5)3]2]- < [F-PBB]-<< [B(C6F5)4]- < [N(CN-PBB)2]-. The anion [N(CN-PBB)2]- gives a catalyst productivity about 2500 times higher than that of [NC-PBB]- and exceeds that of [B(C6F5)4]- based catalysts. The van der Waals volumes and surface areas of the anions have been calculated and provide a rationale for the observed reactivity trends in polymerisation reactions.
RESUMEN
Octahedral titanium and zirconium complexes based on salicyloxazoline ligands with sterically demanding ortho-substituents provide a new family of extremely active ethene polymerization catalysts [up to 10(8) g PE (mol bar h)(-1)] which are in some cases "single site".