30 research outputs found
Penerapan Model Pembelajaran Atraktif Berbasis Multiple Intelligences Tentang Pemantulan Cahaya pada Cermin
Penelitian ini bertujuan untuk mengetahui efektivitas penerapan model pembelajaran atraktif berbasis multiple intelligences dalam meremediasi miskonsepsi siswa tentang pemantulan cahaya pada cermin. Pada penelitian ini digunakan bentuk pre-eksperimental design dengan rancangan one group pretest-post test design. Alat pengumpulan data berupa tes pilihan ganda dengan reasoning. Hasil validitas sebesar 4,08 dan reliabilitas 0,537. Siswa dibagi menjadi lima kelompok kecerdasan, yaitu kelompok linguistic intelligence, mathematical-logical intelligence, visual-spatial intelligence, bodily-khinestetic intelligence, dan musical intelligence. Siswa membahas konsep fisika sesuai kelompok kecerdasannya dalam bentuk pembuatan pantun-puisi, teka-teki silang, menggambar kreatif, drama, dan mengarang lirik lagu. Efektivitas penerapan model pembelajaran multiple intelligences menggunakan persamaan effect size. Ditemukan bahwa skor effect size masing-masing kelompok berkategori tinggi sebesar 5,76; 3,76; 4,60; 1,70; dan 1,34. Penerapan model pembelajaran atraktif berbasis multiple intelligences efektif dalam meremediasi miskonsepsi siswa. Penelitian ini diharapkan dapat digunakan pada materi fisika dan sekolah lainnya
Use of a Bidentate Ligand Featuring an <i>N</i>‑Heterocyclic Phosphenium Cation (NHP<sup>+</sup>) to Systematically Explore the Bonding of NHP<sup>+</sup> Ligands with Nickel
A novel
bidentate ligand featuring an <i>N</i>-heterocyclic phosphenium
cation (NHP<sup>+</sup>) linked to a phosphine side arm is used to
explore the coordination chemistry of NHP<sup>+</sup> ligands with
nickel. Direct P–Cl bond cleavage from a chlorophosphine precursor
[PP]-Cl (<b>1</b>) by NiÂ(COD)<sub>2</sub> affords the asymmetric
bimetallic complex [Cl<sub>2</sub>NiÂ(μ-PP)<sub>2</sub>Ni] (<b>2</b>) via a nonoxidative process. Abstraction of the halide with
either NaBPh<sub>4</sub> or KÂ[BÂ(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] prior to metal coordination to form the free phosphenium ligand
[PP]<sup>+</sup> <i>in situ</i>, followed by coordination
to NiÂ(COD)<sub>2</sub>, afforded the halide-free Ni<sup>0</sup> complexes
[(PP)ÂNiÂ(COD)] [BÂ(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (<b>4</b>) and [(PP)ÂNiÂ(COD)]Â[BPh<sub>4</sub>] (<b>5</b>). Chloride abstraction
from <b>1</b> is problematic in the presence of a PF<sub>6</sub><sup>–</sup> counterion, however, as evident by the formation
of [(PP)ÂNiÂ(PP-F)]Â[PF<sub>6</sub>] (<b>3</b>). The COD ligand
in <b>5</b> can be readily displaced with PMe<sub>3</sub> or
PPh<sub>3</sub> to afford [(PP)ÂNiL<sub>2</sub>]Â[BPh<sub>4</sub>] (L
= PMe<sub>3</sub> (<b>6</b>), PPh<sub>3</sub> (<b>7</b>)). Complexes <b>2</b>–<b>7</b> feature planar
geometries about the NHP<sup>+</sup> phosphorus atom and unusually
short Ni–P distances, indicative of multiple bonding resulting
from both P → Ni σ donation and Ni → P π
backbonding. This bonding description is supported by theoretical
studies using natural bond orbital analysis
Noninnocent Behavior of Bidentate Amidophosphido [NP]<sup>2–</sup> Ligands upon Coordination to Copper
The
synthesis and preliminary coordination chemistry of two new redox-active
bidentate ligands containing amido and phosphido donors are described.
Treatment of the [<sup>R</sup>NP]<sup>2–</sup> (R = Ph, 2,4,6-trimethylphenyl)
ligands with CuCl<sub>2</sub> and PMe<sub>3</sub> results in a dimeric
copperÂ(I) P–P coupled product via ligand oxidation. The intermediate
of this reaction is proposed to involve a ligand radical generated
via oxidation of the [<sup>R</sup>NP]<sup>2–</sup> ligand by
copperÂ(II), and the existence of such an intermediate is probed using
computational methods. Significant radical character on the phosphorus
atoms of the alleged [<sup>R</sup>NP]<sup>•–</sup>/copperÂ(I)
intermediate leads to P–P radical coupling
Cobalt N‑Heterocyclic Phosphenium Complexes Stabilized by a Chelating Framework: Synthesis and Redox Properties
Two cobalt complexes
containing coordinated N-heterocyclic phosphenium
(NHP<sup>+</sup>) ligands are synthesized using a bidentate NHP<sup>+</sup>/phosphine chelating ligand, <b>[PP]</b><sup><b>+</b></sup>. Treatment of NaÂ[CoÂ(CO)<sub>4</sub>] with the chlorophosphine
precursor [PP]Cl (<b>1</b>) affords [PP]ÂCoÂ(CO)<sub>2</sub> (<b>2</b>), which features a planar geometry at the NHP<sup>+</sup> phosphorus center and a short Co–P distance [1.9922(4) Ã…]
indicative of a Coî—»P double bond. The more electron-rich complex
[PP]ÂCoÂ(PMe<sub>3</sub>)<sub>2</sub> (<b>3</b>), which is synthesized
in a one-pot reduction procedure with <b>1</b>, CoCl<sub>2</sub>, PMe<sub>3</sub>, and KC<sub>8</sub>, has an even shorter Co–P
bond [1.9455(6) Ã…] owing to stronger metal-to-phosphorus back-donation.
The redox properties of <b>2</b> and <b>3</b> were explored
using cyclic voltammetry, and oxidation of <b>3</b> was achieved
to afford [[PP]ÂCoÂ(PMe<sub>3</sub>)<sub>2</sub>]<sup>+</sup> (<b>4</b>). The electron paramagnetic resonance spectrum of complex <b>4</b> features hyperfine coupling to both <sup>59</sup>Co and <sup>31</sup>P, suggesting strong delocalization of the unpaired electron
density in this complex. Density functional theory calculations are
used to further explore the bonding and redox behavior of complexes <b>2</b>–<b>4</b>, shedding light on the potential for
redox noninnocent behavior of NHP<sup>+</sup> ligands
Synthesis, Structure, and Reactivity of an Anionic Zr–Oxo Relevant to CO<sub>2</sub> Reduction by a Zr/Co Heterobimetallic Complex
Oxidative addition
of CO<sub>2</sub> to the reduced Zr/Co complex (THF)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co (<b>1</b>) followed
by one-electron reduction leads to formation of an unusual terminal
Zr–oxo anion [<b>2]Â[NaÂ(THF)</b><sub><b>3</b></sub><b>]</b> in low yield. To facilitate further study of this
compound, an alternative high-yielding synthetic route has been devised.
First, <b>1</b> is treated with CO to form (THF)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>CoÂ(CO) (<b>3</b>); then, addition of H<sub>2</sub>O to <b>3</b> leads
to the Zr–hydroxide complex (HO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>CoÂ(CO) (<b>4</b>). Deprotonation
of <b>4</b> with LiÂ(NÂ(SiMe<sub>3</sub>)<sub>2</sub>) leads to
the anionic Zr–oxo species <b>[2]Â[LiÂ(THF)</b><sub><b>3</b></sub><b>]</b> or <b>[2]Â[LiÂ(12-c-4)]</b> in the
absence or presence of 12-crown-4, respectively. The coordination
sphere of the Li<sup>+</sup> countercation is shown to lead to interesting
structural differences between these two species. The anionic oxo
fragment in complex <b>[2]Â[LiÂ(12-c-4)]</b> reacts with electrophiles
such as MeOTf and Me<sub>3</sub>SiOTf to generate (MeO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>CoÂ(CO) (<b>5</b>) and (Me<sub>3</sub>SiO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>CoÂ(CO) (<b>6</b>), respectively,
and addition of acetic anhydride generates (AcO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>CoÂ(CO) (<b>7</b>). Complex <b>[2]Â[LiÂ(12-c-4)]</b> is also shown to bind CO<sub>2</sub> to form a monoanionic Zr–carbonate, [(12-crown-4)ÂLi]Â[(κ<sup>2</sup>-CO<sub>3</sub>)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>CoÂ(CO)] (<b>[8]Â[LiÂ(12-c-4)]</b>). A more
stable version of this compound <b>[8]Â[KÂ(18-c-6)]</b> is formed
when a K<sup>+</sup> counteranion and 18-crown-6 are used. Binding
of CO<sub>2</sub> to <b>[2]Â[LiÂ(12-c-4)]</b> is shown to be reversible
using isotopic labeling studies. In an effort to address methods by
which these CO<sub>2</sub>-derived products could be turned over in
a catalytic cycle, it is shown that the Zr–OMe bond in <b>5</b> can be cleaved using H<sup>+</sup> and the CO ligand can
be released from Co under photolytic conditions in the presence of
I<sub>2</sub>
Interaction and Activation of Carbon–Heteroatom π Bonds with a Zr/Co Heterobimetallic Complex
Single-electron
transfer from the Zr<sup>IV</sup>Co<sup>–I</sup> heterobimetallic
complex (THF)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co-N<sub>2</sub> (<b>1</b>) to benzophenone
was previously shown to result in the isobenzopinacol product [(Ph<sub>2</sub>CO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co-N<sub>2</sub>]<sub>2</sub> (<b>4</b>) via coupling
of two ketyl radicals. Thermolysis of <b>4</b> led to cleavage
of the CO bond to generate a Zr/Co μ-oxo species featuring
an unusual terminal Coî—»CPh<sub>2</sub> carbene linkage (<b>3</b>). In this work monomeric ketyl radical complexes have been
synthesized, and the reactivity of these compounds has been explored.
The electronic preference for the formation of a ketyl radical complex
or a coordination complex has been investigated computationally. Furthermore,
thione substrates were allowed to react with <b>1</b>, generating
new complexes that bind the thione to the Co rather than undergoing
single-electron transfer (<b>12</b>,<b> 14</b>). The preference
of thiones to coordinate to Co can be overridden if the Co is ligated
by CO, in which case a thioketyl radical complex forms (<b>13</b>) analogous to <b>4</b>. The reaction between <b>1</b> and imines resulted in N–H bond activation, affording a μ-methyleneamido
Co–H complex (<b>16</b>) that can undergo cyclometalation
and loss of H<sub>2</sub> (<b>15</b>)
Lewis Acid Catalysis with Cationic Dinuclear Gold(II,II) and Gold(III,III) Phosphorus Ylide Complexes
The
dinuclear goldÂ(II,II) and goldÂ(III,III) complexes [Au<sub>2</sub>(μ-PY)<sub>2</sub>(MeCN)<sub>2</sub>]ÂOTf<sub>2</sub> (<b>2-OTf</b><sub><b>2</b></sub>) and [Au<sub>2</sub>(μ-PY)<sub>2</sub>(μ-CH<sub>2</sub>)Â(MeCN)<sub>2</sub>]ÂOTf<sub>2</sub> (<b>3-OTf</b><sub><b>2</b></sub>) (PY = [(CH<sub>2</sub>)<sub>2</sub>PPh<sub>2</sub>]<sup>−</sup>) have been synthesized
and evaluated as Lewis acid catalysts for Mukaiyama addition and alkyne
hydroamination reactions. <b>2-OTf</b><sub><b>2</b></sub> and <b>3-OTf</b><sub><b>2</b></sub> provide similar
or improved catalytic activity for these reactions compared to the
commonly used goldÂ(I) Lewis acids Ph<sub>3</sub>PAuOTf and IPrAuOTf.
The versatile Lewis acidity of <b>2-OTf</b><sub><b>2</b></sub> was further demonstrated by its superior performance in a
cascade reaction involving intramolecular hydroamination followed
by intermolecular conjugate addition to generate a 2,3-substituted
indole
Stoichiometric Cî—»O Bond Oxidative Addition of Benzophenone by a Discrete Radical Intermediate To Form a Cobalt(I) Carbene
Single
electron transfer from the Zr<sup>III</sup>Co<sup>0</sup> heterobimetallic
complex (THF)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co–N<sub>2</sub> (<b>1</b>) to benzophenone was
previously shown to result in the isobenzopinacol
product [(Ph<sub>2</sub>CO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co–N<sub>2</sub>]<sub>2</sub> (<b>2</b>) via coupling of two ketyl radicals. In this work, thermolysis of <b>2</b> in an attempt to favor a monomeric ketyl radical species
unexpectedly led to cleavage of the C–O bond to generate a
Zr/Co μ-oxo species featuring an unusual terminal Coî—»CPh<sub>2</sub> carbene linkage, (η<sup>2</sup>-MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)ÂZrÂ(μ-O)Â(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>2</sub>Coî—»CPh<sub>2</sub> (<b>3</b>). This complex was characterized structurally and spectroscopically,
and its electronic structure is discussed in the context of density
functional theory calculations. Complex <b>3</b> was also shown
to be active toward carbene group transfer (cyclopropanation), and
silane addition to <b>3</b> leads to PhSiH<sub>2</sub>O–ZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co–N<sub>2</sub> (<b>5</b>) via a proposed Co–alkyl bond homolysis
route
Cobalt N‑Heterocyclic Phosphenium Complexes Stabilized by a Chelating Framework: Synthesis and Redox Properties
Two cobalt complexes
containing coordinated N-heterocyclic phosphenium
(NHP<sup>+</sup>) ligands are synthesized using a bidentate NHP<sup>+</sup>/phosphine chelating ligand, <b>[PP]</b><sup><b>+</b></sup>. Treatment of NaÂ[CoÂ(CO)<sub>4</sub>] with the chlorophosphine
precursor [PP]Cl (<b>1</b>) affords [PP]ÂCoÂ(CO)<sub>2</sub> (<b>2</b>), which features a planar geometry at the NHP<sup>+</sup> phosphorus center and a short Co–P distance [1.9922(4) Ã…]
indicative of a Coî—»P double bond. The more electron-rich complex
[PP]ÂCoÂ(PMe<sub>3</sub>)<sub>2</sub> (<b>3</b>), which is synthesized
in a one-pot reduction procedure with <b>1</b>, CoCl<sub>2</sub>, PMe<sub>3</sub>, and KC<sub>8</sub>, has an even shorter Co–P
bond [1.9455(6) Ã…] owing to stronger metal-to-phosphorus back-donation.
The redox properties of <b>2</b> and <b>3</b> were explored
using cyclic voltammetry, and oxidation of <b>3</b> was achieved
to afford [[PP]ÂCoÂ(PMe<sub>3</sub>)<sub>2</sub>]<sup>+</sup> (<b>4</b>). The electron paramagnetic resonance spectrum of complex <b>4</b> features hyperfine coupling to both <sup>59</sup>Co and <sup>31</sup>P, suggesting strong delocalization of the unpaired electron
density in this complex. Density functional theory calculations are
used to further explore the bonding and redox behavior of complexes <b>2</b>–<b>4</b>, shedding light on the potential for
redox noninnocent behavior of NHP<sup>+</sup> ligands
Stoichiometric Cî—»O Bond Oxidative Addition of Benzophenone by a Discrete Radical Intermediate To Form a Cobalt(I) Carbene
Single
electron transfer from the Zr<sup>III</sup>Co<sup>0</sup> heterobimetallic
complex (THF)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co–N<sub>2</sub> (<b>1</b>) to benzophenone was
previously shown to result in the isobenzopinacol
product [(Ph<sub>2</sub>CO)ÂZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co–N<sub>2</sub>]<sub>2</sub> (<b>2</b>) via coupling of two ketyl radicals. In this work, thermolysis of <b>2</b> in an attempt to favor a monomeric ketyl radical species
unexpectedly led to cleavage of the C–O bond to generate a
Zr/Co μ-oxo species featuring an unusual terminal Coî—»CPh<sub>2</sub> carbene linkage, (η<sup>2</sup>-MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)ÂZrÂ(μ-O)Â(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>2</sub>Coî—»CPh<sub>2</sub> (<b>3</b>). This complex was characterized structurally and spectroscopically,
and its electronic structure is discussed in the context of density
functional theory calculations. Complex <b>3</b> was also shown
to be active toward carbene group transfer (cyclopropanation), and
silane addition to <b>3</b> leads to PhSiH<sub>2</sub>O–ZrÂ(MesNP<sup><i>i</i></sup>Pr<sub>2</sub>)<sub>3</sub>Co–N<sub>2</sub> (<b>5</b>) via a proposed Co–alkyl bond homolysis
route