swadhinmandal.com | catalysis

Our research is primarily focused on developing concepts for metal-free catalytic processes that utilize p-electrons. Traditional catalytic processes heavily rely on d-electrons from rare, expensive, and often toxic transition metals. In contrast, our approach aims to harness p-electrons for various important organic transformations. For example, we have developed methods to achieve C-C and C-N cross-coupling reactions based on redox processes utilizing p-electrons. In this direction, we are exploring various low-valent organo-main group species for their effectiveness in catalytic CO2 reduction and functionalization, enabling the production of valuable products without the use of transition metal-based catalysts.

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Research Highlights

Amit Biswas

Creating Superhot Electrons

with Light

Sreejyothi P.

Main-group Elements as Alternatives

to Transition Metals

Subir Maji
A Sustainable Way
to Transform CO2 into Olefins

Swagata Sil

Transition Metal-free C-N

Coupling at Room Temperature

Arpan Das

Discovering New Reactions

with CO2

Vera Koester from ChemistryViews talks to
Swadhin Mandal

Prof . Swadhin Mandal Delivered a lecture on Mimicking Transition Metals

Significant Publications:

Datta et al, Organophotocatalytic Redox-Neutral Strategy for Late-Stage Drug Functionalization with SO2 Gas. Chem. Sci. 2025, 16,5064–5075.
Biswas et al, A BOIMPY Dye Enables Multi-Photoinduced Electron Transfer Catalysis: Reaching Super-reducing Properties. Angew. Chem. Int. Ed. 2025, 64, e202416472.
Maji et al, Independent LUMO Reactivity in Mesoionic N-Heterocyclic Thiones: Synthesis of a Stable Radical Anion. Angew. Chem. Int. Ed. 2025, 64, e202418673.
Sreejyothi et al, Transition Metal-Mimicking Relay Catalysis by a Low-Valent Phosphorus Compound. J. Am. Chem. Soc. 2024, 146, 16743−16752.
Maji et al, Metal-Free Organocatalytic S-Formylation of Thiols using CO2. Nature Catalysis 2024, 7, 375-385.
Sil et al, Cross-coupling between Aryl Halides and Aryl Alkynes Catalyzed by an Odd Alternant Hydrocarbon. Chemistry- A European Journal 2024, e202400895.
Das et al, Highly Stable Self-Regenerating Organic Multi-Redox Systems derived from Bicyclic (Alkyl)(amino)carbenes (BICAACs). Chem. Eur. J. 2024, e202303411.
Datta et al, Uncovericng the On-pathway Reaction Intermediates for Metal-Free Atom Transfer Radical Addition to Olefins through Photogenerated Phenalenyl Radical Anion. ACS Catalysis 2024, 14, 3420-3433

Gautam et al, Bicyclic (alkyl)(amino)carbene (BICAAC) in Dual Role: Activation of Primary Amides and CO2 towards Catalytic N-Methylation. Chemical Science 2023, 14, 5079-5086.
Biswas et al, Mechanochemical Solid State Single Electron Transfer from Reduced Organic Hydrocarbon for Catalytic Aryl-halide Bond Activation. Chemical Science 2023, 14, 2606-2615.

Sil et al, Reduced Phenalenyl Based Molecule as a Super Electron Donor for Radical Mediated C-N Coupling Catalysis at Room Temperature. J. Am. Chem. Soc. 2022, 144, 49, 22611–22621.
Das et al, Mesoionic N-Heterocyclic Imines as Super Nucleophiles in Catalytic Coupling of Amides by CO2. Angew. Chem. Int. Ed. 2022, 61, e202213614.

Ahmed J and Mandal S K, Phenalenyl Radical: Smallest Polycyclic Odd Alternant Hydrocarbon Present in the Graphene Sheet. Chemical Reviews, 2022, 122, 13, 11369–11431

Banik et al, Tuning Redox States of Phenalenyl Based Molecule by Consecutive Reduction towards Transition Metal-Free Heck-type C-C Cross-Coupling. ACS Catal. 2022, 12, 5000−5012
Maji et al, Mesoionic N-heterocyclic Olefin Catalysed Reductive Functionalization of CO2 for Consecutive N-Methylation of Amines. Chemical Science, 2021, 12, 12174-12180
Sreejyothi et al, An NHC-stabilized Phosphinidene for Catalytic Formylation: A DFT Guided Approach. Chem. Eur. J. 2021, 27, 11656 –11662 (Hot Paper)
Banik et al, Mimicking Transition Metals in Borrowing Hydrogen from Alcohol. Chemical Science, 2021, 12, 8353-8361

Ahmed et al, Switching between mono- and doubly-reduced odd alternant hydrocarbon: Designing redox catalyst. Chemical Science, 2021, 12, 3039-3049
Das et al, A Bottleable Imidazole-Based Radical as a Single Electron Transfer Reagent. J. Org. Chem., 2021, 86, 1, 1246–1252

Sreejyothi P and Swadhin K Mandal, From CO2 Activation to Catalytic Reduction: A Metal-free Approach. Chemical Science, 2020, 11, 10571-10593
Sau et al. Stable Abnormal N-Heterocyclic Carbenes and their Applications in Catalysis. Chem. Soc. Rev., 2020, 49, 1233-1252
Bhunia et al. Transition Metal-Free Catalytic Reduction of Primary Amides Using an Abnormal NHC based Potassium Complex: Integrating Nucleophilicity with Lewis Acidic Activation. Chemical Science, 2020, 11, 1848-1854
Gupta et al. Computationally designed antibody–drug conjugates self-assembled via affinity ligands. Nature Biomed. Eng., 2019, 3, 917–929 (2019)
Ahmed et al. A K-Arylacetylide Complex for Catalytic Terminal Alkyne Functionalization using KOtBu as a Precatalyst. Chem. Commun., 2019, 55, 13860-13863
Bhunia et al. Storing redox equivalent in the phenalenyl backbone towards catalytic multi-electron reduction. Chemical Science, 2019, 10, 7433-7441
Sau et al. Transforming Atmospheric CO2 into Alternative Fuels: a Metal-Free Approach under Ambient Conditions. Chemical Science, 2019, 10, 1879-1884
Ahmed et al. Integrating Organic Lewis Acid and Redox Catalysis: The Phenalenyl Cation in Dual Role. J. Am. Chem. Soc., 2018, 140, 8330-8339. (This work was highlighted by Nature India, Chemistryworld.)
Hota et al. Metal-Free Catalytic Formylation of Amides Using CO2 under Ambient Conditions. ACS Catal., 2018, 8, 12, 11999-12003.
Vijaykumar et al. Tuning Redox Non-innocence of Phenalenyl Ligand toward Efficient Nickel-Assisted Catalytic Hydrosilylation. Chemical Science, 2018, 9, 2817-2825.
Ahmed et al. New Face of Phenalenyl Based Radical in Transition Metal Free C-H Arylation of Heteroarenes at Room Temperature: Trapping the Radical Initiator via C-C σ Bond Formation. Chemical Science, 2017, 8, 7798-7806.
Mukherjee et al. Exploring Closed-Shell Cationic Phenalenyl: From Catalysis to Spin Electronics. Acc. Chem. Res., 2017, 50, 1679–1691.
Gupta et al. Development of an antibody-drug conjugate platform using platinum as a linker. Chemical Science, 2017, 8, 2387-2395.
Sau et al. Metal Free Reduction of CO2 to Methoxyborane Under Ambient Conditions through Borondiformate Formation. Angew. Chem. Int. Ed., 2016, 55, 15147 –15151.
Pariyar et al. Switching Closed-Shell to Open-Shell Phenalenyl: Toward Designing Electroactive Materials. J. Am. Chem. Soc., 2015, 137, 5955-5960
Raha Roy et al. Phenalenyl in Different Role: Catalytic Activation through the Nonbonding Molecular Orbital. ACS Catal., 2014, 4, 4307–4319
Raman et al. Interface-engineered templates for molecular spin memory devices. Nature , 2013, 493, 509-513
Santra et al. Palladium Nanoparticles on Graphite Oxide: Highly Recyclable Catalyst for the Synthesis Biaryl Cores. ACS Catal., 2013, 3, 2776−2789.
Mukherjee et al. Assembling Zirconium and Calcium Moieties through an Oxygen Center for Intramolecular Hydroamination Reaction: A Single System for Double Activation. Angew. Chem. Int. Ed. 2011, 50, 3968–3972 (Hot Paper)

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