Weakly interacting solvation spheres surrounding a calixarene-protected tetrairidium carbonyl cluster: contrasting effects on reactivity of alkane solvent and silica support

Palermo, Andrew P.; Zhang, Shengjie; Hwang, Son-Jong; Dixon, David A.; Gates, Bruce C.; Katz, Alexander

doi:10.1039/c8dt01371c

Weakly interacting solvation spheres surrounding a calixarene-protected tetrairidium carbonyl cluster: contrasting effects on reactivity of alkane solvent and silica support

Journal Article · Fri Aug 24 00:00:00 EDT 2018 · Dalton Transactions

DOI:https://doi.org/10.1039/c8dt01371c· OSTI ID:1609503

^[1]; Zhang, Shengjie ^[2]; ^[3]; ^[2]; ^[4]; ^[5]

Univ. of California, Davis, CA (United States); Univ. of California, Berkeley, CA (United States); DOE/OSTI
Univ. of Alabama, Tuscaloosa, AL (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Univ. of California, Davis, CA (United States)
Univ. of California, Berkeley, CA (United States)

The tetrairidium carbonyl cluster Ir₄L₃(CO)₉ (L = tert-butyl-calix[4]arene(OPr)₃(OCH₂PPh₂) (Ph = phenyl; Pr = propyl)) on a partially dehydroxylated silica support undergoes hydrogen activation at a rate and with a mechanism different from those pertaining to the cluster in alkane solution. These results are unobvious in view of the sterically bulky ligands protecting the cluster and the nearly identical CO band frequencies in the infrared spectra characterizing the supported and dissolved Ir₄L₃(CO)₉, both before reaction and during reaction involving decarbonylation in the presence of either helium or H₂ (and H₂ reacted with the clusters to form hydrides with the same Ir–H band frequencies for clusters in alkane solvent and supported on silica). The initial rates of CO loss from the supported clusters in the presence of helium were the same as those in the presence of H₂. In this work, the comparison demonstrates that the rate-determining step for hydride formation on the silica-supported cluster is CO dissociation. In contrast, the comparable dissociation of CO from the cluster in n-decane solution requires a higher temperature, 343 K, and is at least an order of magnitude slower than when the clusters were supported on silica. CO dissociation is not the rate-determining step for hydrogen activation on the cluster in n-decane, as the rate is influenced by reactant H₂ as well.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of California, Davis, CA (United States); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-04ER15513; FG02-05ER15696

OSTI ID:: 1609503

Alternate ID(s):: OSTI ID: 1469718

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 38 Vol. 47; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Weakly interacting solvation spheres surrounding a calixarene-protected tetrairidium carbonyl cluster: contrasting effects on reactivity of alkane solvent and silica support

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