Structural characterization of [M,C,2H]+ products formed by reaction of 5d metal cations Pt+ and Ir+ with ethylene oxide and Ta+ with methane using messenger spectroscopy

C–H Bond Activation and C–C Coupling of Methane on a Single Cationic Platinum Center: A Spectroscopic and Theoretical Study

“…It must be noted that as in a previous publication, the b -type transition associated with the in-plane C–H wagging vibration (denoted with an asterisk in Figure 2 c) was calculated at 748 cm –1 (unscaled) but has been shifted down by 40 cm –1 before scaling by 0.97 to better match the observed spectrum. 18 …”

“…In such studies, it was found that several third-row TM cations are capable of dehydrogenating methane at room temperature. 7 − 18 The structures of several [TM,C,2H] + products were recently identified using infrared multiple-photon dissociation (IRMPD) action spectroscopy. Comparisons to theory identified TM + –CH 2 carbene structures for Ta + , W + (both with agostic distortions), and Pt + (having the classic C 2v structure), and H–TM + –CH hydrido carbyne structures for Os + and Ir + , where reaction with the latter metal ion also yielded a minority carbene product.…”

“…In recent years, there have been many investigations of how transition metals (TMs) interact with methane. − Studying these systems under well-defined conditions with highly sensitive mass-spectrometric methods can offer detailed information on reaction mechanisms and the electronic structure needed on the metal center that allows facile C–H bond activation. In such studies, it was found that several third-row TM cations are capable of dehydrogenating methane at room temperature. − The structures of several [TM,C,2H] + products were recently identified using infrared multiple-photon dissociation (IRMPD) action spectroscopy. Comparisons to theory identified TM + –CH 2 carbene structures for Ta + , W + (both with agostic distortions), and Pt + (having the classic C 2v structure), and H–TM + –CH hydrido carbyne structures for Os + and Ir + , where reaction with the latter metal ion also yielded a minority carbene product. ,− In 1990, Irikura and Beauchamp observed that several of these third-row TM cations could also dehydrogenate multiple methane molecules, presumably by oligomerization. ,, For Pt + , they reported dehydrogenation of up to five methane molecules but only characterized the first step, i.e., Pt + + CH 4 → PtCH 2 + + H 2 as facile.…”

IR Spectroscopic Characterization of Methane Adsorption on Copper Clusters Cun+ (n = 2–4)

“…Reactions between metal ions and clusters with methane have been studied extensively. − Because of their electrophilic nature, positively charged ions are generally more reactive toward CH 4 than neutrals or anions . Products formed when reacting atomic metal ions M + and methane have been widely studied using optical spectroscopy to uncover their structures. − Possible binding motifs cover the spectrum from η 3 for electrostatic dominated interactions and η 2 for orbital interactions, to C–H activation and subsequent H 2 elimination yielding a [M,C,2H] + product that can adopt carbene or hydrido carbyne structures. Experimental structural information on reaction products involving cationic clusters is more limited.…”

Study on the methane dehydrogenation reaction catalyzed by triangular transition metal: a theoretical research

“…In recent years, many studies have been conducted on how transition metals interact with methane [18][19][20]. In these studies, it was found that several triple transition metal cations can dehydrogenate methane at room temperature [21][22][23][24][25][26][27][28][29][30][31][32]. Since the early 1990s, theoretical quantum computing has led the progress of methane conversion.…”