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1. The Prototypical Transition Metal Carbenes, (CO) ₅ Cr=CH ₂ , (CO) ₄ Fe=CH ₂ , (CO) ₃ Ni=CH ₂ , (CO) ₅ Mo=CH ₂ , (CO) ₄ Ru=CH ₂ , (CO) ₃ Pd=CH ₂ , (CO) ₅ W=CH ₂ , (CO) ₄ Os=CH ₂ , and (CO) ₃ Pt=CH ₂ : Challenge to Experiment

   https://doi.org/10.1021/acs.jpca.8b05394  

   Weidman, Jared D.; Estep, Marissa L.; Schaefer, Henry F. (July 2018, The Journal of Physical Chemistry A)
2. Heterogeneous Electrocatalysts for Metal–CO ₂ Batteries and CO ₂ Electrolysis

   https://doi.org/10.1021/acsenergylett.2c02445  

   Wang, Jianda; Marchetti, Barbara; Zhou, Xiao-Dong; Wei, Shuya (April 2023, ACS Energy Letters)
3. H and CO Co-Induced Roughening of Cu Surface in CO ₂ Electroreduction Conditions

   https://doi.org/10.1021/jacs.4c03515  

   Zhang, Zisheng; Gee, Winston; Sautet, Philippe; Alexandrova, Anastassia N (June 2024, Journal of the American Chemical Society)
4. Reduction-induced CO dissociation by a [Mn(bpy)(CO) ₄ ][SbF ₆ ] complex and its relevance in electrocatalytic CO ₂ reduction

   https://doi.org/10.1039/c9dt04150h  

   Kuo, Hsin-Ya; Tignor, Steven E.; Lee, Tia S.; Ni, Danrui; Park, James Eujin; Scholes, Gregory D.; Bocarsly, Andrew B. (January 2020, Dalton Transactions)

   [Mn(bpy)(CO) 3 Br] is recognized as a benchmark electrocatalyst for CO 2 reduction to CO, with the doubly reduced [Mn(bpy)(CO) 3 ] − proposed to be the active species in the catalytic mechanism. The reaction of this intermediate with CO 2 and two protons is expected to produce the tetracarbonyl cation, [Mn(bpy)(CO) 4 ] + , thereby closing the catalytic cycle. However, this species has not been experimentally observed. In this study, [Mn(bpy)(CO) 4 ][SbF 6 ] ( 1 ) was directly synthesized and found to be an efficient electrocatalyst for the reduction of CO 2 to CO in the presence of H 2 O. Complex 1 was characterized using X-ray crystallography as well as IR and UV-Vis spectroscopy. The redox activity of 1 was determined using cyclic voltammetry and compared with that of benchmark manganese complexes, e.g. , [Mn(bpy)(CO) 3 Br] ( 2 ) and [Mn(bpy)(CO) 3 (MeCN)][PF 6 ] ( 3 ). Infrared spectroscopic analyses indicated that CO dissociation occurs after a single-electron reduction of complex 1 , producing a [Mn(bpy)(CO) 3 (MeCN)] + species. Complex 1 was experimentally verified as both a precatalyst and an on-cycle intermediate in homogeneous Mn-based electrocatalytic CO 2 reduction. 

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5. Ion-induced surface reactions and deposition from Pt(CO) ₂ Cl ₂ and Pt(CO) ₂ Br ₂

   https://doi.org/10.3762/bjnano.15.115  

   Abdel-Rahman, Mohammed K; Eckhert, Patrick M; Chaudhary, Atul; Johnson, Johnathon M; Yu, Jo-Chi; McElwee-White, Lisa; Fairbrother, D Howard (January 2024, Beilstein Journal of Nanotechnology)

   Ion beam-induced deposition (IBID) using Pt(CO)₂Cl₂and Pt(CO)₂Br₂as precursors has been studied with ultrahigh-vacuum (UHV) surface science techniques to provide insights into the elementary reaction steps involved in deposition, complemented by analysis of deposits formed under steady-state conditions. X-ray photoelectron spectroscopy (XPS) and mass spectrometry data from monolayer thick films of Pt(CO)₂Cl₂and Pt(CO)₂Br₂exposed to 3 keV Ar⁺, He⁺, and H₂⁺ions indicate that deposition is initiated by the desorption of both CO ligands, a process ascribed to momentum transfer from the incident ion to adsorbed precursor molecules. This precursor decomposition step is accompanied by a decrease in the oxidation state of the Pt(II) atoms and, in IBID, represents the elementary reaction step that converts the molecular precursor into an involatile PtX₂species. Upon further ion irradiation these PtCl₂or PtBr₂species experience ion-induced sputtering. The difference between halogen and Pt sputter rates leads to a critical ion dose at which only Pt remains in the film. A comparison of the different ion/precursor combinations studied revealed that this sequence of elementary reaction steps is invariant, although the rates of CO desorption and subsequent physical sputtering were greatest for the heaviest (Ar⁺) ions. The ability of IBID to produce pure Pt films was confirmed by AES and XPS analysis of thin film deposits created by Ar⁺/Pt(CO)₂Cl₂, demonstrating the ability of data acquired from fundamental UHV surface science studies to provide insights that can be used to better understand the interactions between ions and precursors during IBID from inorganic precursors. 

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