4 research outputs found
Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation
The hydrosilylation reaction is one
of the largest-scale application
of homogeneous catalysis and is widely used to enable the commercial
manufacture of silicon products. However, considerable issues including
disposable platinum consumption, undesired side reactions and unacceptable
catalyst residues still remain. Here, we synthesize a heterogeneous
partially charged single-atom platinum supported on anatase TiO<sub>2</sub> (Pt<sub>1</sub><sup>δ+</sup>/TiO<sub>2</sub>) catalyst
via an electrostatic-induction ion exchange and two-dimensional confinement
strategy, which can catalyze hydrosilylation reaction with almost
complete conversion and produce exclusive adduct. Density functional
theory calculations reveal that unexpected property of Pt<sub>1</sub><sup>δ+</sup>/TiO<sub>2</sub> originates from atomic dispersion
of active species and unique partially positive charge Pt<sup>δ+</sup> electronic structure that conventional nanocatalysts do not possess.
The fabrication of single-atom Pt<sub>1</sub><sup>δ+</sup>/TiO<sub>2</sub> catalyst accomplishes a reasonable use of Pt through recycling
and maximum atom-utilized efficiency, indicating the potential to
achieve a green hydrosilylation industry
Heterogeneous Rhodium Single-Atom-Site Catalyst Enables Chemoselective Carbene N–H Bond Insertion
Transition-metal-catalyzed carbene insertion reactions
of a nitrogen–hydrogen
bond have emerged as robust and versatile methods for the construction
of C–N bonds. While significant progress of homogeneous catalytic
metal carbene N–H insertions has been achieved, the control
of chemoselectivity in the field remains challenging due to the high
electrophilicity of the metal carbene intermediates. Herein, we present
an efficient strategy for the synthesis of a rhodium single-atom-site
catalyst (Rh-SA) that incorporates a Rh atom surrounded by three nitrogen
atoms and one phosphorus atom doped in a carbon support. This Rh-SA
catalyst, with a catalyst loading of only 0.15 mol %, exhibited exceptional
catalytic performance for heterogeneous carbene insertion with various
anilines and heteroaryl amines in combination with diazo esters. Importantly,
the heterogeneous catalyst selectively transformed aniline derivatives
bearing multiple nucleophilic moieties into single N–H insertion
isomers, while the popular homogeneous Rh2(OAc)4 catalyst produced a mixture of overfunctionalized side products.
Additionally, similar selectivities for N–H bond insertion
with a set of stereoelectronically diverse diazo esters were obtained,
highlighting the general applicability of this heterogeneous catalysis
approach. On the basis of density functional theory calculations,
the observed selectivity of the Rh-SA catalyst was attributed to the
insertion barriers and the accelerated proton transfer assisted by
the phosphorus atom in the support. Overall, this investigation of
heterogeneous metal-catalyzed carbene insertion underscores the potential
of single-atom-site catalysis as a powerful and complementary tool
in organic synthesis
Heterogeneous Rhodium Single-Atom-Site Catalyst Enables Chemoselective Carbene N–H Bond Insertion
Transition-metal-catalyzed carbene insertion reactions
of a nitrogen–hydrogen
bond have emerged as robust and versatile methods for the construction
of C–N bonds. While significant progress of homogeneous catalytic
metal carbene N–H insertions has been achieved, the control
of chemoselectivity in the field remains challenging due to the high
electrophilicity of the metal carbene intermediates. Herein, we present
an efficient strategy for the synthesis of a rhodium single-atom-site
catalyst (Rh-SA) that incorporates a Rh atom surrounded by three nitrogen
atoms and one phosphorus atom doped in a carbon support. This Rh-SA
catalyst, with a catalyst loading of only 0.15 mol %, exhibited exceptional
catalytic performance for heterogeneous carbene insertion with various
anilines and heteroaryl amines in combination with diazo esters. Importantly,
the heterogeneous catalyst selectively transformed aniline derivatives
bearing multiple nucleophilic moieties into single N–H insertion
isomers, while the popular homogeneous Rh2(OAc)4 catalyst produced a mixture of overfunctionalized side products.
Additionally, similar selectivities for N–H bond insertion
with a set of stereoelectronically diverse diazo esters were obtained,
highlighting the general applicability of this heterogeneous catalysis
approach. On the basis of density functional theory calculations,
the observed selectivity of the Rh-SA catalyst was attributed to the
insertion barriers and the accelerated proton transfer assisted by
the phosphorus atom in the support. Overall, this investigation of
heterogeneous metal-catalyzed carbene insertion underscores the potential
of single-atom-site catalysis as a powerful and complementary tool
in organic synthesis
Confined Pyrolysis within Metal–Organic Frameworks To Form Uniform Ru<sub>3</sub> Clusters for Efficient Oxidation of Alcohols
Here we report a novel approach to
synthesize atomically dispersed
uniform clusters via a cage-separated precursor preselection and pyrolysis
strategy. To illustrate this strategy, well-defined Ru<sub>3</sub>(CO)<sub>12</sub> was separated as a precursor by suitable molecular-scale
cages of zeolitic imidazolate frameworks (ZIFs). After thermal treatment
under confinement in the cages, uniform Ru<sub>3</sub> clusters stabilized
by nitrogen species (Ru<sub>3</sub>/CN) were obtained. Importantly,
we found that Ru<sub>3</sub>/CN exhibits excellent catalytic activity
(100% conversion), high chemoselectivity (100% for 2-aminobenzaldehyde),
and significantly high turnover frequency (TOF) for oxidation of 2-aminobenzyl
alcohol. The TOF of Ru<sub>3</sub>/CN (4320 h<sup>–1</sup>)
is about 23 times higher than that of small-sized (ca. 2.5 nm) Ru
particles (TOF = 184 h<sup>–1</sup>). This striking difference
is attributed to a disparity in the interaction between Ru species
and adsorbed reactants