Metal-Free Photoinduced Divergent Activation of N2O and H2 Employing Main-Group Radical Pairs

Abstract

Activating robust small molecules like nitrous oxide (N2O) and molecular hydrogen (H2) without transition metals is a key challenge in sustainable chemistry. To address this, we developed an efficient photochemical platform that uses silylphosphanes to divergently activate both the gases. Under photoirradiation, the silylphosphane’s P-Si bond undergoes rapid homolytic cleavage, releasing highly reactive silyl and phosphinyl radicals. When exposed to N2O, these independent radicals act parallelly to drive a double-deoxygenation cascade, yielding the corresponding tetra-aryldiphosphine dioxide and siloxane. Remarkably, this same transient radical pair can also activate H2 under exceptionally mild conditions. Supported by control experiments and DFT studies that confirm a purely radicaldriven mechanism, this work highlights main-group radical pair as a powerful, sustainable alternative to precious-metal catalysis.

Metal–Ligand Cooperative Control of Reactivity in a Porphyrin Manganese(IV)–Oxo–Phenoxyl Radical Complex for Water Activation
Adelais Trapali, Rongning Lin, Georgios Charalambidis +7
ChemistryEurope9 Sep 2026Peer-reviewedCC BY 4.0Full textInorganic & organometallic chemistryHAL
Photoinduced C–S Cleavage in Thiols and Oligopeptides to Initiate Controlled Radical Polymerization
Sophie M. Mazure, Paula B. Melton, Nathan G. Blackwell +2
ChemRxiv30 Oct 2026PreprintLicence not statedGeneral chemistryChemRxiv
A photoinduced, FeX3-catalyzed, stereo- and regio-selective halofunctionalization of olefins with MXn via a radical-polar crossover reaction
Jing Huang, Yidong Liu, Shen Li +7
Communications Chemistry10 Oct 2026Peer-reviewedCC BY-NC-ND 4.0Full textOrganic chemistryCrossref
Photoinduced Redox Initiation System for Delayed-Onset Radical UV-Curable Adhesives on Opaque Substrates.
Naoya Machida, Ataru Daimon, Daisuke Aoki +1
ACS macro letters1 Oct 2026Peer-reviewedCC BYFull textOrganic chemistryEurope PMC
Photoredox/Pyridine N-Oxide Catalyzed Acyl Radical Generation From Aldehydes for Divergent Synthesis of Pyrroles and Carbocyclic Ketones.
Saranya Vadakke Poikayil Sasi, Lindsey Soruco, Yongming Deng
Advanced synthesis & catalysis8 Sep 2026Peer-reviewedCC BYFull textOrganic chemistryEurope PMC

Cite

BibTeX RIS

BibTeX

@misc{mondal2026metalfree,
  title = {{Metal-Free Photoinduced Divergent Activation of N2O and H2 Employing Main-Group Radical Pairs}},
  author = {Reetu Rani Mondal and Rahul Mondal and K. Geetharani and Geetharani K},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010163/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010163/v1},
  note = {CC BY},
}

RIS

TY  - UNPB
TI  - Metal-Free Photoinduced Divergent Activation of N2O and H2 Employing Main-Group Radical Pairs
AU  - Reetu Rani Mondal
AU  - Rahul Mondal
AU  - K. Geetharani
AU  - Geetharani K
PY  - 2026
DA  - 2026/10/09
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010163/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010163/v1
AB  - Activating robust small molecules like nitrous oxide (N2O) and molecular hydrogen (H2) without transition metals is a key challenge in sustainable chemistry. To address this, we developed an efficient photochemical platform that uses silylphosphanes to divergently activate both the gases. Under photoirradiation, the silylphosphane’s P-Si bond undergoes rapid homolytic cleavage, releasing highly reactive silyl and phosphinyl radicals. When exposed to N2O, these independent radicals act parallelly to drive a double-deoxygenation cascade, yielding the corresponding tetra-aryldiphosphine dioxide and siloxane. Remarkably, this same transient radical pair can also activate H2 under exceptionally mild conditions. Supported by control experiments and DFT studies that confirm a purely radicaldriven mechanism, this work highlights main-group radical pair as a powerful, sustainable alternative to precious-metal catalysis.
ER  -

Abstract

Related

Cite