Modifying Methylalumoxane via Alkyl Exchange
| dc.contributor.author | Zijlstra, Harmen S. | |
| dc.contributor.author | Joshi, Anuj | |
| dc.contributor.author | Linnolahti, Mikko | |
| dc.contributor.author | Collins, Scott | |
| dc.contributor.author | McIndoe, J. Scott | |
| dc.date.accessioned | 2018-11-26T14:40:36Z | |
| dc.date.copyright | 2018 | en_US |
| dc.date.issued | 2018 | |
| dc.description.abstract | Methylalumoxane (MAO) ionizes highly selectively in the presence of octamethyltrisiloxane (OMTS) to generate [Me2Al∙OMTS]+ [(MeAlO)16(Me3Al)6Me]–. We can take advantage of this transformation to examine the reactivity of a key component of MAO using electrospray ionization mass spectrometry (ESI-MS), and here we describe the reactivity of this pair of ions with other trialkyl aluminum (R3Al) components. Using continuous injection methods, we found Et3Al to exchange much faster and extensively at room temperature in fluorobenzene (t½ ~ 2 sec, up to 25 exchanges of Me for Et) than iBu3Al (t½ ~ 40 sec, up to 11 exchanges) or Oct3Al (t½ ~ 200 sec, up to 7 exchanges). The exchanges are reversible and the methyl groups on the cation are also observed to exchange with the added R3Al species. These results point to the reactive components of MAO having a structure that deviates significantly from the cage-like motifs studied to date. | en_US |
| dc.description.embargo | 2019-11-21 | |
| dc.description.reviewstatus | Reviewed | en_US |
| dc.description.scholarlevel | Faculty | en_US |
| dc.description.sponsorship | We thank NOVA Chemicals’ Centre for Applied Research for financial support and useful discussions. We thank Albemarle Corp. for a kind donation of 10 and 30 wt% MAO, and Dr. Bill Beard for helpful discussions. J.S.M. thanks NSERC (Strategic Project Grant # 478998-15) for operational funding and CFI, BCKDF, and the University of Victoria for infrastructural support. S.C. acknowledges support for a visiting scientist position from the University of Victoria. The computations were made possible by use of the Finnish Grid Infrastructure and Finnish Grid and Cloud Infrastructure resources (urn:nbn:fi:research-infras-2016072533). | en_US |
| dc.identifier.citation | Zijlstra, H.S., Joshi, A., Linnolahti, M., Collins, S. & McIndoe, J.S. (2018). Modifying Methylalumoxane via Alkyl Exchange. Dalton Transactions, 0(0), xx. http://dx.doi.org/10.1039/C8DT04242J | en_US |
| dc.identifier.uri | https://doi.org/10.1039/C8DT04242J | |
| dc.identifier.uri | http://hdl.handle.net/1828/10363 | |
| dc.language.iso | en | en_US |
| dc.publisher | Dalton Transactions | en_US |
| dc.subject | Methylalumoxane | en_US |
| dc.subject | Activators | en_US |
| dc.subject | Aluminum Alkyls | en_US |
| dc.subject | Mass Spectrometry | en_US |
| dc.subject | Homogeneous Catalysis | en_US |
| dc.title | Modifying Methylalumoxane via Alkyl Exchange | en_US |
| dc.type | Postprint | en_US |