Infrared and manometric evidence for the formation of the [Ag(CO)3]+ complex ion at high PCO

Rack, Jeffrey J.; Moasser, Bahram; Gargulak, Jerry D.; Gladfelter, Wayne L.; Hochheimer, H. D.; Strauss, Steven H.

doi:10.1039/c39940000685

Cited by 34 publications

(31 citation statements)

References 10 publications

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“…4). 25,26,45 This is in excellent agreement with the work by the Strauss group 25,26,45 The non-classical nature of the Pd +2 (CO)2 cation also explains why its vibrational frequencies are similar for a range of zeolites. The unique 0.85 nm in diameter cavity in SSZ-13 seems to be a great stabilizer for such species.…”

Section: Resultssupporting

confidence: 84%

Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite

Khivantsev

Jaegers²,

Koleva³

et al. 2019

Preprint

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We provide the first observation and characterization of super-electrophilic metal cations on a solid support. For Pd/SSZ-13 the results of our combined experimental (FTIR, XPS, HAADF-STEM) and density functional theory study reveal that Pd ions in zeolites, previously identified as Pd +3 and Pd +4 , are in fact present as super electrophilic Pd +2 species (charge-transfer complex/ion pair with the negatively charged framework oxygens). In this contribution we re-assign the spectroscopic signatures of these species, discuss the unusual coordination environment of "naked" (ligandfree) super-electrophilic Pd +2 in SSZ-13, and their complexes with CO and NO. With CO, non-classical, highly positive [Pd(CO)2] 2+ ions are formed with the zeolite framework acting as a weakly coordinating anion (ion pairs). Non-classical carbonyl complexes also form with Pt +2 and Ag + in SSZ-13. The Pd +2 (CO)2 complex is remarkably stable in zeolite cages even in the presence of water. Dicarbonyl and nitrosyl Pd +2 complexes, in turn, serve as precursors to the synthesis of previously inaccessible Pd +2 -carbonyl-olefin [Pd(CO)(C2H4)] and -nitrosyl-olefin [Pd(NO)(C2H4)] complexes. Overall, we show that zeolite framework can stabilize super electrophilic metal (Pd) cations, and show the new chemistry of Pd/SSZ-13 system with implications for adsorption and catalysis.

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Section: Resultssupporting

confidence: 84%

Stabilization of Super Electrophilic Pd+2 Cations in Small-Pore SSZ-13 Zeolite

Khivantsev

Jaegers²,

Koleva³

et al. 2019

Preprint

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“…Open Information, the average Ag:Li atomic composition ratio is approximately 1:0.05, similar to that of the FCC AgLi 0.05 phase 52 . The corresponding Li site occupancy is therefore taken as 0.05.…”

Section: Chemical Science Accepted Manuscriptsupporting

confidence: 55%

“…49,50 However, positively charged Ag + -CO is characterized with stronger blue-shift to 2150-2200 cm −1 due to the lesser degree of electron back-donation. 51,52 Our Ag/SBA-15 shows an adsorption peak at 2026 cm −1 , which can be attributed to the linear adsorption of CO on Ag 0 . As lithium ion content increases, the CO adsorption peak gradually moves to higher wavenumbers (from 2026 cm −1 to 2037 cm −1 ), indicating the consistent electron transfer from Ag surface to Li + dopant that can give higher activity in this hydrogenation reaction.…”

Section: Electronic Effectmentioning

confidence: 95%

Intercalating lithium into the lattice of silver nanoparticles boosts catalytic hydrogenation of carbon–oxygen bonds

Duan

Chen

et al. 2021

Chem. Sci.

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“…7, adding Ni resulted in the shift of linear bands to a higher wavenumber (from 2026 cm 1 to 2035 cm -1 to 2037 cm 1 ), suggesting electron transfer from Ni to Ag. The range of the CO absorption peak position of Ag 0 CO was 2020-2050 cm 1 [37,38], whereas that of Ag + CO was 2150-2200 cm 1 [43,44]. Hence, the Ag species possessed a higher IR wavenumber with higher valence state.…”

Section: Ft-ir Study Of Co Absorbed On Catalystsmentioning

confidence: 89%