Organometallics
Article
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(16) Mixed ligand compositions designed to enforce catalyst site
isolation and likely catalyst loadings were estimated as follows. The
channel diameter in the IRMOF-74-III structure is about 20 Å, and the
tethered catalyst extends about 10 Å into the channel, as shown in
Figure 1. Layers of linkers lining the channels in this structure are
separated by 6.5 Å, and the thickness of the tethered catalyst measured
along the channel axis is about 13 Å. Nearest neighbor contacts
between tethered catalysts can in principal be avoided if each catalyst
“blocks” access to all other linkers in the same layer and all linkers in
the two adjacent layers. In this case, only 1/9 (11%) of the linkers
could bear amine groups in a perfectly ordered structure. However, the
mixed linker structure is almost certainly not ordered, and shorter
separations between neighboring functionalized linkers will almost
certainly occur. Consider the present case where only 10% of the
linkers are functionalized. In a completely disordered structure, two
types of disorder can occur. First, there is a 10% probability that each
of the 6 + 5 + 6 = 17 nearest neighbor linkers to each amine-
functionalized linker will be another amine-functionalized linker.
Second, there is a 50% chance that each amine-functionalized
phenylene groups will occupy one of the two possible rotameric
configurations. This means that there is still a (1/10)(17)(1/2) = 17/
20 (85%) probability of a “blocked” site being occupied by another
amine-functionalized ligand and only a 3/20 (15%) probability that a
“blocked” site will not be occupied.
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Zhizhko, P. A. Chem. Rev. 2016, 116, 323−421. (c) For an overview of
postpolymerization modification see: Gunay, K. A.; Theato, P.; Klok,
H.-A. In Functional Polymers by Post-Polymerization Modification:
Concepts, Guidelines, and Applications; Theato, P., Klock, H.-A., Eds.;
Wiley-VCH: Weinheim, 2013; pp 1−44.
(6) Consider, for example, the remarkably reactive and selective
asymmetric catalysts obtained by postsynthetic metalation of MOF
linkers derived from 1,1′-bi-2-naphthol (BINOL) using Ti(OiPr)4.7a
Here, a titanium loading measurement was reported, revealing that at
most 68 mol % of the titanium present could be assigned to the
desired Ti(BINOL) catalyst, with a least 32 mol % arising from
undesired side reactions. In a related Ti(BINOL) catalyst,7b at least 40
mol % of the titanium present arose from side reactions. The side
reactions presumably arose from titanium alkoxide hydrolysis/
condensation: in both cases the MOF precursors contained far more
water than BINOL groups, and Ti(OiPr)4 is extremely moisture
sensitive, forming polytitanates upon exposure to water.8
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et, C.; Comas-Vives, A.; Conley, M. P.;
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Alkoxo and Aryloxo Derivatives of Metals; Academic Press: San Diego,
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(20) (a) Hanson, P. R.; Maitra, S.; Chegondi, R.; Markley, J. L. In
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(c) van Lierop, B. J.; Lummiss, J. A. M.; Fogg, D. E. In Olefin
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