About

Kyle M. Lancaster is the Stephanie Czech Rader ‘37 Professor in Chemistry at Cornell University, affiliated with the Department of Chemistry and Chemical Biology within the College of Arts and Sciences. His research employs synthesis, biochemistry, and a broad range of spectroscopic methods—including synchrotron-based core spectroscopies—to explore reactivity mediated by transition metal complexes and metalloenzymes. His group currently focuses on transformations relevant to the biogeochemical nitrogen cycle and C–H functionalization, contributing to understanding and addressing climate change and nitrogen cycling processes. Lancaster's academic background includes a postdoctoral fellowship at Cornell University, a PhD in Chemistry from the California Institute of Technology, and a BA in Molecular Biology from Pomona College. His work has earned numerous awards and honors, such as the Society of Biological Inorganic Chemistry Early Career Award, fellowship of the Royal Society of Chemistry, and the Sloan Research Fellowship. His research has significantly advanced the understanding of bioinorganic chemistry, particularly in the context of nitrogen cycle chemistry, transition metal electronic structure, and catalysis.

Research topics

• Chemistry
• Inorganic chemistry
• Organic chemistry
• Crystallography
• Atomic physics
• Quantum mechanics
• Physics

Selected publications

• Ammonia monooxygenase: a work in progress

  Chemical Science · 2026-01-01

  articleOpen accessSenior authorCorresponding

  OH, the structure and genetic underpinnings of this chemical behavior vary significantly. Further, there are many Cu-binding sites in AMO, and consequently there has been substantial discussion regarding the nature of the Cu site or sites responsible for substrate activation. Overall, AMO has largely eluded direct study because active protein has only recently been purified due to difficulties in cultivation of the native organism and recalcitrance of the protein to recombinant expression. This review is intended to serve as a primer to AMO, yielding the necessary context to understand its importance.

  PublisherOA PDFDOI

• Bioinorganic Chemistry of Nitrification: Structure and Function of Ammonia Monooxygenase (Final Technical Report)

  2026-01-12

  reportOpen access1st authorCorresponding
  PublisherOA PDFDOI

• Accessing Square Planar Cobalt Nitrenoid Redox Isomers across Three Oxidation States

  Journal of the American Chemical Society · 2025-07-15 · 4 citations

  articleCorresponding

  The bonding structures of cobalt nitrenoid complexes are fundamental to their reactivity across various transformations. However, unraveling the electronic configuration of these highly covalent Co–N interactions remains a significant challenge. In this study, we present the synthesis and electronic structure elucidation of a cobalt nitrenoid series in the underexplored square planar ligand field. Using a structurally rigid pincer-type platform and arylazides as the nitrene source, a suite of terminal metal nitrenoids featuring formal Co(III/IV/V) centers and electronically distinct aryl substituents was isolated and structurally characterized. Cyclic voltammetry analysis establishes a linear free energy relationship between their reduction potentials and the electronic properties of nitrene substituents. A combination of spectroscopic and computational methods was employed to probe the electronic structures of the cobalt nitrenoid series, including electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations. The result suggests that on the continuum of metal nitrenoid redox isomerism─ranging from metal imide (NR2–) to imidyl radical (2NR–) to nitrene adduct (1NR/3NR) formulations─the isolated formal Co(III/IV/V) complexes feature predominantly [Co(II)–2NR–], [Co(III)–2NR–]+, and [Co(III)–1NR]2+ characters, respectively.

  PublisherDOI

• Metal–Metal Bonding Influences Hydride Reactivity in [Sn–Rh]³⁺ and [Sn–Ni]²⁺ Bimetallics

  Journal of the American Chemical Society · 2025-09-29 · 1 citations

  articleSenior author

  center acting as a potential dihydrogen activator. Targeting the introduction of a hydride ligand to the bimetallic core, our reactivity studies have revealed a preference for the hydride ligand to be bound to the Rh center, instead of the Sn center. Examination of the electronic structures of these complexes via theoretical and experimental methods has revealed the electron acceptor nature of the Rh center within the bimetallic core and offers an explanation for the localization of the hydride between metal centers.

  PublisherDOI

• Carbon Dioxide Capture and Functionalization from a Molecular Ti(III) Oxo Anion

  Angewandte Chemie · 2025-08-25

  articleOpen access

  Abstract Carbon dioxide capture and functionalization sequesters carbon dioxide in more robust products and offers a viable route to reducing greenhouse gas emissions. We present herein a unique molecular Ti III oxo anion that reversibly binds CO 2 to allow both its sequestration and functionalization. The reduction of [(PN) 2 Ti═O] ( 1 ) [PN = (2‐P i i Pr 2 ‐4‐methylphenyl)(mesityl)amide] with KC 8 and 2.2.2‐cryptand (crypt) resulted in formation of [K(crypt)][(PN) 2 Ti═O] ( 2 ), which was fully characterized and shown to contain a Ti‐centered radical. Complex 2 reacts with Al(CH 3 ) 3 to form [K(crypt)][(PN) 2 Ti{O(Al(CH 3 ) 3 }] ( 3 ), which can be independently prepared from [K(crypt)][(PN) 2 Ti(OCP)] and Al(CH 3 ) 3 . Whereas 1 does not react with CO 2 , 2 rapidly captures the gas (1 atm, 25 °C) to produce a Ti III carbonate [K(crypt)][(PN) 2 Ti(κ 2 ‐O 2 C═O)] ( 4 ). Chemical and electrochemical oxidation of 4 releases CO 2 to regenerate 1 while a soluble organic carbonate [Me 3 SiOC(O)OSiMe 3 , Me = CH 3 ] is obtained from reaction of 4 with ClSiMe 3 .

  PublisherDOI

• Divergent Reactivity of Azides and Diazoalkanes Toward Ferrous Complexes and Isolation of a Fe^III Carbene Radical Complex

  Organometallics · 2025-01-09 · 2 citations

  articleCorresponding

  Treatment of [(tBupyrr2pyr)Fe(OEt2)] (1-OEt2) (tBupyrr2pyr2– = 3,5-tBu2-bis(pyrrolyl)pyridine) with trimethylsilyl azide (N3SiMe3) and subsequent photolysis at 390 nm results in clean formation of [(tBupyrrpyrpyrrNHSiMe3)Fe] (2) as the result of a nitrene being inserted into a tert-butyl C–H bond of the tBupyrr2pyr ligand. Treatment of 1-OEt2 with azidotrimethyltin (N3SnMe3), however, results in isolation of the γ-bound azide adduct ferrous complex, [(tBupyrr2pyr)Fe(N3SnMe3)] (1-N3SnMe3). When treated with diphenyl diazomethane (Ph2CN2), complex 1-OEt2 converts to the iron carbene complex [(tBupyrr2pyr)FeCPh2] (1-CPh2), and the X-ray structure revealed a Fe–CPh2 bond length of 1.964(3) Å. A room temperature magnetic moment of 1-CPh2 indicates an S = 2 spin state, consistent with a high-spin FeIII center antiferromagnetically coupled to a carbene radical anion (CPh2•–). Zero-field 57Fe Mössbauer spectroscopy and Fe K-edge X-ray absorption spectroscopy confirm this assignment. In solution, complex 1-CPh2 rearranges to [{tBupyrrpyrC(═CPh2)-C(CMe3)═CH–C(CMe3)═N}Fe]2 (3) resulting from carbene insertion into the 1-position of the pyrrolide arm of the tBupyrr2pyr ligand and dimerization. Complex 3 possesses two high-spin FeII centers according to 57Fe Mössbauer spectroscopy, with antiferromagnetic coupling between the spin centers. Monitoring the conversion of 1-CPh2 to 3 by UV–vis spectroscopy reveals this process to be first order in 1-CPh2 with a highly ordered transition state evidenced by activation parameters: ΔS‡ = −87.6 ± 25.8 J·mol–1·K–1 and ΔH‡ = 63.1 ± 8.3 kJ·mol–1.

  PublisherDOI

• Nitrous oxide production via enzymatic nitroxyl from the nitrifying archaeon <i>Nitrosopumilus maritimus</i>

  Proceedings of the National Academy of Sciences · 2025-01-17 · 12 citations

  articleOpen accessSenior authorCorresponding

  Ammonia oxidizing archaea (AOA) are among the most abundant microorganisms on earth and are known to be a major source of nitrous oxide (N 2 O) emissions, although biochemical origins of this N 2 O remain unknown. Enzymological details of AOA nitrogen metabolism are broadly unavailable. We report the recombinant expression, purification, and characterization of a multicopper oxidase, Nmar_1354, from the AOA Nitrosopumilus maritimus . We show that Nmar_1354 selectively produces nitroxyl (HNO) by coupling the oxidation of the obligate nitrification intermediate hydroxylamine (NH 2 OH) to dioxygen (O 2 ) reduction. This HNO undergoes several downstream reactions, although the major fates are production of N 2 via reaction with NH 2 OH and dimerization with itself to yield N 2 O. These results afford one plausible enzymatic origin for N 2 O release by AOA. Moreover, these results reveal a physiologically relevant enzymatic reaction for producing HNO, an enigmatic nitrogen oxide speculated to be operative in cellular signaling and in energy transduction.

  PublisherOA PDFDOI

• Single-site ruthenium catalyst supported on zeolite for CO ₂ hydrogenation to methyl formate

  Science Advances · 2025-04-16 · 4 citations

  articleOpen access

  Technologies for the transformation of atmospheric CO 2 to useful chemicals, such as formic acid (FA), are essential to combatting excessive fossil fuel use and will need to be implemented on large scale. However, hydrogenation of CO 2 to (base-free) FA is challenging for heterogeneous catalysts, due to the requirement for low temperatures enforced by the entropically unfavorable reaction of gases. By coupling CO 2 hydrogenation to esterification, methyl formate (MF) can be prepared as a promising alternative platform chemical. Herein, a robust, heterogeneous single-metal-site catalyst was prepared and shown to achieve methanol hydrocarboxylation rates superior to nanoparticle catalysts (up to 18.3 ± 0.6 mmol hour −1 <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" overflow="scroll"> <mml:mrow> <mml:msubsup> <mml:mi mathvariant="bold">g</mml:mi> <mml:mtext>cat</mml:mtext> <mml:mrow> <mml:mo mathvariant="bold-italic">−</mml:mo> <mml:mn mathvariant="bold">1</mml:mn> </mml:mrow> </mml:msubsup> </mml:mrow> </mml:math> ) while maintaining very high selectivity to MF (≥95%). Characterization reveals isolated, monodisperse Ru-nitrosyl complexes bound to three O-atoms of the zeolite framework, and the robust catalyst formed achieves a cumulative turnover number of more than 3500 over eight cycles. This work pushes the boundaries of supported single-site catalysts in CO 2 utilization.

  PublisherDOI

• Titanium Phosphinidene and Phosphide Moieties from Oxidative Phosphorylation and Desilylation

  Journal of the American Chemical Society · 2025-03-28 · 6 citations

  article

  A unique entry into mononuclear titanium complexes bearing phosphinidene and phosphide ligand moieties is reported. Reaction of [K(crypt)][(PN)2TiCl] (1, crypt = 2.2.2-cryptand) with [Na(OCP)] results in [K(crypt)][(PN)2Ti(OCP)] (2) and such species can be oxidized to the derivative [(PN)2Ti(OCP)] (3), both of which do not undergo decarbonylation. However, the reaction of 1 and [NaP(SiMe3)2] leads to an unprecedented TiIII phosphinidene, [K(crypt)][(PN)2Ti═PSiMe3] (4), through an oxidative phosphorylation reaction. To promote the formation of a Ti≡P bond, complex 4 was treated with 0.5 equivalent XeF2, resulting in an oxidative desilylation step forming a molecular titanium phosphide complex, [K(crypt)][(PN)2Ti≡P] (5), which showed a characteristic downfield chemical shift at 1449.8 pmm in the 31P NMR spectrum. Complex 5 can be further functionalized to generate a terminal TiIV phosphinidene, [(PN)2Ti═PSiMe3] (6), and the latter can be independently accessed through oxidation of 4. All new complexes were characterized structurally and as appropriate by multinuclear NMR, CW X-band EPR (for TiIII), and HFEPR (for TiII) spectroscopies.

  PublisherDOI

• Carbon Dioxide Capture and Functionalization from a Molecular Ti(III) Oxo Anion

  Angewandte Chemie International Edition · 2025-08-25 · 2 citations

  articleOpen access

  Abstract Carbon dioxide capture and functionalization sequesters carbon dioxide in more robust products and offers a viable route to reducing greenhouse gas emissions. We present herein a unique molecular Ti III oxo anion that reversibly binds CO 2 to allow both its sequestration and functionalization. The reduction of [(PN) 2 Ti═O] ( 1 ) [PN = (2‐P i i Pr 2 ‐4‐methylphenyl)(mesityl)amide] with KC 8 and 2.2.2‐cryptand (crypt) resulted in formation of [K(crypt)][(PN) 2 Ti═O] ( 2 ), which was fully characterized and shown to contain a Ti‐centered radical. Complex 2 reacts with Al(CH 3 ) 3 to form [K(crypt)][(PN) 2 Ti{O(Al(CH 3 ) 3 }] ( 3 ), which can be independently prepared from [K(crypt)][(PN) 2 Ti(OCP)] and Al(CH 3 ) 3 . Whereas 1 does not react with CO 2 , 2 rapidly captures the gas (1 atm, 25 °C) to produce a Ti III carbonate [K(crypt)][(PN) 2 Ti(κ 2 ‐O 2 C═O)] ( 4 ). Chemical and electrochemical oxidation of 4 releases CO 2 to regenerate 1 while a soluble organic carbonate [Me 3 SiOC(O)OSiMe 3 , Me = CH 3 ] is obtained from reaction of 4 with ClSiMe 3 .

  PublisherOA PDFDOI

Recent grants

• Bioinorganic Chemistry of Nitrogen

  NIH · $3.0M · 2017–2028

• SusChEM: CAREER: High-Resolution X-ray Spectroscopic Studies of Base Metal Catalysis

  NSF · $561k · 2015–2020

• CAS: Collaborative Research: Electronic Structure/Function Relationships Underpinning Atom Transfer Reactivity

  NSF · $366k · 2023–2026

• NIH Grant P41RR001209

  NIH · $12.9M · 2015

• CAS: Collaborative Research: Electronic Structure/Function Relationships in Base Metal Complexes Spanning the Oxo/Oxene and Imide/Nitrene Continuum

  NSF · $300k · 2020–2023

Frequent coauthors

• Ida M. DiMucci

  156 shared

• Samantha N. MacMillan

  Cornell University

  112 shared

• Stephen Sproules

  University of Glasgow

  88 shared

• Serena DeBeer

  Max Planck Institute for Chemical Energy Conversion

  59 shared

• Dennis Nordlund

  Stanford Synchrotron Radiation Lightsource

  54 shared

• Charles J. Titus

  National Institute of Standards and Technology

  49 shared

• James T. Lukens

  44 shared

• Patrick L. Holland

  Yale University

  44 shared

Labs

• Lancaster GroupPI

Awards & honors

• 2024 Society of Biological Inorganic Chemistry Early Career…
• 2023 Fellow of the Royal Society of Chemistry
• 2022 Morgan Chia-Wen Sze and Bobbi Josephine Hernandez Disti…
• 2019 National Fresenius Award – Phi Lambda Upsilon/American…
• 2018 Kavli Fellow – National Academy of Sciences