Cerium-Hydride Secondary Building Units in a Porous Metal-Organic Framework for Catalytic Hydroboration and Hydrophosphination

Article abstract of DOI:10.1021/jacs.6b10055

We report the stepwise, quantitative transformation of Ce^IV₆(μ₃-O)₄(μ₃-OH)₄(OH)₆(OH₂)₆ nodes in a new Ce-BTC (BTC = trimesic acid) metal-organic framework (

Full text of DOI:10.1021/jacs.6b10055

Subscriber access provided by CORNELL UNIVERSITY LIBRARY
Communication
Cerium-Hydride Secondary Building Units in a Porous Metal-Organic
Framework for Catalytic Hydrobo-ration and Hydrophosphination
Pengfei Ji, Takahiro Sawano, Zekai Lin, Ania Urban, Dean Boures, and Wenbin Lin
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b10055 • Publication Date (Web): 28 Oct 2016
Downloaded from http://pubs.acs.org on October 28, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Cerium-Hydride Secondary Building Units in a Porous Metal-Organic
Framework for Catalytic Hydroboration and Hydrophosphination
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Pengfei Ji†, Takahiro Sawano†, Zekai Lin, Ania Urban, Dean Boures, and Wenbin Lin*
Department of Chemistry, University of Chicago, 929 E 57th St, Chicago, IL 60637, USA
activity and unique regioselectivity, likely a result of its low steric
hindrance and electron density compared to existing homogeneꢀ
ous lanthanide catalysts.
ABSTRACT: We report the stepwise, quantitative transforꢀ
mation of CeIV
(
ꢀ
3ꢀO)4(
BTC (BTC = trimesic acid) metalꢀorganic framework (MOF) into
the first CeIII
3ꢀO)4( 3ꢀOLi)4(H)6(THF)6 metalꢀhydride nodes
ꢀ3ꢀOH)4(OH)6(OH2)6 nodes in a new Ceꢀ
6
CeꢀBTC was synthesized in 54% yield by treating
(NH4)2Ce(NO3)6 with H3BTC in a mixture of DMF and H2O at
100 °C (Figure 1a). The structure of CeꢀBTC was modeled using
the crystal structure of ZrꢀBTC (MOFꢀ808) by elongating the Ceꢀ
(
ꢀ
ꢀ
6
that effectively catalyze hydroboration and hydrophophination
reactions. CeHꢀBTC displays low steric hindrance and electron
density compared to homogeneous organolanthanide catalysts,
which likely accounts for the unique 1,4ꢀregioselectivity for the
hydroboration of pyridine derivatives. MOF nodes can thus be
directly transformed into novel singleꢀsite solid catalysts without
homogeneous counterparts for sustainable chemical synthesis.
ꢀ
3ꢀO distance to 2.25 Å (from a Zrꢀꢀ
3ꢀO distance of 2.16 Å).17
Similarities between powder Xꢀray diffraction (PXRD) patterns of
asꢀsynthesized CeꢀBTC and the simulated pattern confirmed the
spn topology (Figure 1b). We believe that the Ce centers possess
square antiprismatic geometry, with a composition of [(ꢀ3ꢀO)2(ꢀ3ꢀ
ꢀ
OH)2(ꢀ2ꢀCO2 )2]Ce(OH)(OH2) (see below), similar to the Zr coꢀ
ordination in MOFꢀ808. As Ce4+ has a larger ionic radius than
Zr4+ [r(Ce4+)=0.97 Å and r(Zr4+)=0.84 Å], the Ce6 node in Ceꢀ
BTC is larger than the Zr6 node in MOFꢀ808, with a CeꢀCe disꢀ
tance of 3.74 Å vs the ZrꢀZr distance of 3.57 Å.
Lanthanide (Ln) catalysts are used for a wide range of reacꢀ
tions, including polymerization,1 hydroamination,2 hydrogenaꢀ
tion,1c,2c hydroboration,2c,3 DielsꢀAlder reactions,1c,4 and Aldol
reactions.1c,5 They are more naturally abundant, less toxic, and
more tolerant of certain functional groups, such as phosphines,
than precious metal catalysts.1c While most lanthanide catalysts
are based on La, Sm, and Lu, little effort has been devoted to
designing effective catalysts based on Ce, which is not only
cheaper and more abundant, but also broadly applied in stoichioꢀ
metric organic transformations.6 Furthermore, Ln catalysts are
often supported on sterically hindered ligands such as η5ꢀC5Me5
(Cp*) to prevent oligomerization and disproportionation, which
restricts the ability to fineꢀtune their electronic and steric properꢀ
ties. Although some elaborately designed ligands, such as
Me2Si(Cp*)2, can increase the open space around Ln centers, they
typically require lengthy and laborious syntheses.7 We thus aimed
to develop new synthetic strategies to produce Ln catalysts with
low steric hindrance and different electronic properties.
Metalꢀorganic frameworks (MOFs) provide a unique approach
to developing highly active, reusable, singleꢀsite solid catalysts
based on molecular species8 via direct solvothermal synthesis9 or
postꢀsynthetic functionalization.10 All components of MOFs, inꢀ
cluding their inorganic nodes,11 organic linkers,12 and void spacꢀ
es,13 have been used to install catalytic species. In particular,
straightforward functionalization of MOF nodes provides an intriꢀ
guing opportunity to design singleꢀsite solid catalysts that do not
have homogeneous counterparts. To date, however, the applicaꢀ
tions of MOF nodes have mostly focused on Lewis or Brønsted
acid catalysts14 or as ligand sites that support other catalytic speꢀ
cies.11,15
N2 sorption isotherms of CeꢀBTC at 77 K gave a Brunauerꢀ
EmmettꢀTeller (BET) surface area of 1008 m2/g and a largest pore
size of 22 Å, which corresponds well to the size of the hexagonal
pore in the simulated structure of CeꢀBTC (Figure 1a). The Ce
oxidation state of CeꢀBTC was studied by Xꢀray adsorption nearꢀ
edge spectroscopy (XANES) and compared to (NH4)2CeIV(NO3)6
and CeIIICl3 standards. CeꢀBTC shows two XANES peaks at 5730
and 5738 eV (Figure 2b), which are identical to the CeIV standard,
indicating the +4 oxidation state in CeꢀBTC. We attributed the
stability of CeIV toward potential reductants, including DMF and
water, to carboxylate coordination.6b 1H NMR of digested Ceꢀ
BTC in D3PO4/DMSOꢀd6 showed only the peaks of H3BTC and
adsorbed solvents, consistent with the coordination of H2O and
OHꢀ to CeIV (Figure S7, SI). Extended Xꢀray adsorption fineꢀ
structure (EXAFS) fitting of the Ce region supported the proposed
structural model, with a CeꢀOH/CeꢀOH2 average distance of 2.43
Å, close to typical Ce(IV)ꢀO distances (Figure S3, SI).18
The Ce coordination environment of [(ꢀ3ꢀO)2(ꢀ3ꢀOH)2(ꢀ2ꢀCO2
ꢀ
)2]Ce(OH)(OH2) in CeꢀBTC is analogous to those of Cp2Ln(X)(L)
(X = anionic ligand and L = neutral ligand) which have been used
in many catalytic reactions. A structural model of CeꢀBTC indiꢀ
cates that CeꢀOH and CeꢀOH2 moieties point toward the large
channel, affording low steric hindrance around the Ce centers.
We thus sought to activate the Ce(OH)(OH2) sites to prepare acꢀ
tive Ce catalysts that are readily accessible to organic substrates
via the large open channels of CeꢀBTC.
Herein we report the direct transformation of CeIV
(
ꢀ3ꢀO)4(
ꢀ3ꢀ
6
OH)4(OH)6(OH2)6 nodes in a new CeꢀBTC (BTC = trimesic acid)
MOF into previously unknown CeIII
(ꢀ3ꢀO)4(ꢀ3ꢀOLi)4(H)6(THF)6
6
metalꢀhydride nodes within the MOF16 and their use in the cataꢀ
lytic hydroboration of pyridines and alkenes, as well as the hyꢀ
drophosphination of alkenes. The CeHꢀBTC catalyst exhibits high
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
tion occurred via an H/OH exchange between HBpin and
Ce(OH)2 to form CeIV(H)2 and HOBpin, followed by bimetallic
reductive elimination of H2 from neighboring CeIV(H)2 species to
form CeIIIH(THF). XANES of CeHꢀBTC showed a single Ce
peak at 5726 eV, identical to the absorption feature of CeCl3
(Figure 2b). Treatment of CeHꢀBTC with hydrochloric acid genꢀ
erated 0.98±0.11 equiv. of H2, while no H2 was observed when
CeꢀBTC or CeOHꢀBTC was treated with hydrochloric acid (Figꢀ
ure S13, SI). The PXRD pattern of CeHꢀBTC is identical to that
of CeꢀBTC, indicating that the MOF framework remains intact
after lithiation and reduction (Figure 1b). EXAFS fitting at the Ce
edge corresponded to our proposed CeH(THF) coordination modꢀ
el, with an Rꢀfactor of 0.015 (Figure 2c). EXAFS fitting afforded
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
a CeIIIꢀ(
ꢀ3ꢀO) distance of 2.44 Å in CeHꢀBTC, slightly longer
than the CeIVꢀ(
ꢀ3ꢀO) distance of 2.25 Å in CeOHꢀBTC, which is
consistent with the increase of Ce ionic radius upon reduction.6b
ꢀ
We expect that the [(
ꢀ3ꢀO)2(
ꢀ3ꢀOH)2(
ꢀ
2ꢀCO2 )2]Ce moiety is less
electronꢀrich than other organolanthanide fragments, such as
Cp*2Ln, potentially endowing the CeHꢀBTC catalyst with unique
activity and selectivity.
Figure 1. (a) Synthesis and a structural model of the CeꢀBTC
MOF (b) Similarities between the PXRD patterns of CeꢀBTC
(red), CeOHꢀBTC (blue), CeHꢀBTC recovered from hydroboraꢀ
tion of pyridine (pink and green) and hydroboration of styrene
indicate the retention of crystallinity after activation and catalysis.
CeꢀBTC was activated by sequential deprotonation with
LiCH2SiMe3 and reduction with pinacolborane (HBpin) to generꢀ
ate the first MOFꢀsupported Ceꢀhydride catalyst for several imꢀ
portant organic transformations (Figure 2a). The lithiated MOF,
denoted CeOHꢀBTC, was obtained by treating CeꢀBTC with 10
equiv. of LiCH2SiMe3 (w.r.t. Ce), which deprotonated (
ꢀ3ꢀ
OH)Ce(OH)(OH2) to form [( 3ꢀOLi)Ce(OH)2]Li and SiMe4. After
ꢀ
removing CeOHꢀBTC, 1.74±0.15 equiv. of SiMe4 (w.r.t. Ce) was
detected in the supernatant by 1H NMR, which corresponded well
to the calculated result of 1.67 (Figure S9, SI). Inductively couꢀ
pled plasmaꢀmass spectrometry (ICPꢀMS) analysis of CeOHꢀBTC
gave a LiꢀtoꢀCe ratio of 1.69±0.05, also matching our calculated
result of 1.67.
CeOHꢀBTC was reduced to form CeHꢀBTC by treatment with
°
HBpin at 60 C in THF for 6 h (Figure 2a). GC analysis of the
head space gas indicated the production of 0.5 equiv. of H2 (w.r.t.
Ce). After removal of CeHꢀBTC, 2.02±0.14 equiv. of HOBpin
1
(w.r.t. Ce) was detected in the supernatant by H NMR, which
corresponded to our calculated result (2 equiv.) (Figure S11, SI).
We confirmed the identity of HOBpin using 11B NMR (δ = 22.7
ppm, 128 MHz) (Figure S10, SI). Based on the formation of 0.5
equiv. of H2 and 2 equiv. of HOBpin, we propose that the reducꢀ
Figure 2. (a) Activation of CeꢀBTC to form CeHꢀBTC. (b)
XANES analysis of CeꢀBTC (blue), CeOHꢀBTC (pink), and CeHꢀ
BTC (green) shows the reduction of CeIV in CeOHꢀBTC to CeIII
2
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
in CeHꢀBTC. (c) XAFS fitting on CeHꢀBTC confirms the proꢀ
posed structure for the catalytic species. The R factor is 0.0146.
2
3
0.5
1
79
99
1
2
3
4
5
6
7
8
9
CeHꢀBTC demonstrates high activity for several catalytic reacꢀ
tions and distinct selectivities from other lanthanide catalysts.
Because 1,4ꢀdihydropyridine is an important building block of
natural products,19 biologically active intermediates,20 and reducꢀ
ing reagents,21 we tested the activity of CeHꢀBTC for the hydrobꢀ
oration of pyridines with HBpin (Chart 1). Although hydroboraꢀ
tion of pyridines provides a convenient synthetic route to 1,4ꢀ
dihydropyridines, only one organoborane catalyst and one rutheꢀ
nium catalyst were reported to effect 1,4ꢀselective hydroboration
reactions.22,23 Reaction of pyridine with HBpin with 4 mol%
4b
1
90
5b
1
1
97
56
6b,c
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
b
c
aNMR yield using CH3NO2 as an internal standard. 36 h. 100
°C.
°
CeHꢀBTC catalyst loading at 80 C for 36 h selectively gave the
1,4ꢀaddition product in 71% yield.24 The hydroboration of pyriꢀ
dines by CeHꢀBTC has a broad substrate scope. With 2 or 4 mol%
catalyst loading, CeHꢀBTC was able to convert 3ꢀbromopyridine
and 3ꢀmethylpyridine to their corresponding 1,4ꢀaddition products
along with small amounts of 1,2ꢀaddition products. We could also
hydroborate 3,5ꢀdisubstututed pyridines, such as 3,5ꢀ
dimethylpyridine, with 10 mol% CeHꢀBTC. CeHꢀBTC also exꢀ
hibited good hydroboration activity for quinoline.
Hydrophosphination of alkenes is a powerful, direct, and atomꢀ
economical method for obtaining organophosphines,26 an imꢀ
portant class of compounds for chemical, agrochemical, pharmaꢀ
ceutical industries.27 Moreover, organophosphines are among the
most important ligands in homogeneous catalysis. While several
examples of hydrophosphination of alkenes have been reported,
the scope of substrates is limited, and examples of hydrophosꢀ
phination of unactivated aliphatic olefins are rare.28 CeHꢀBTC
catalyzed hydrophosphination of various unactivated alkenes. At
4 mol% Ceꢀloading, hydrophosphination of 1ꢀoctene for 18 h
yielded 74% of nꢀoctyldiphenylphosphine (entry 1, Table 2). Proꢀ
longing the reaction to 5 d afforded the addition product in 99%
yield (entry 2, Table 2). Hydrophosphination also proceeded for
1ꢀdecene and 6ꢀchlorohexene (entries 3 and 4, Table 2). CeHꢀ
BTC displayed good activity for 2ꢀmethylꢀ1ꢀpentene, an αꢀ
substituted alkene (entry 5, Table 2). The hydrophosphination of
cisꢀβꢀmethylstyrene with HPPh2 gave 41% of the addition product
(entry 6, Table 2).
Chart 1: CeHꢀBTC Catalyzed 1,4ꢀSelective Hydroboration of
Pyridine Derivativesa
Table 2. CeHꢀBTC Catalyzed Hydrophosphination of Alkenes
Entry
Substrate
Product
Cat. Loading Yield
(mol% Ce)
4
(%)a
74
1b
2
a
b
4
4
99
75
NMR yield based on mesitylene as an internal standard; 110
°C.
3
4
5
CeHꢀBTC is also active in the hydroboration of alkenes, a useꢀ
ful catalytic reaction in organic synthesis.25 Reacting styrene and
1.5 eq. of HBpin with 0.1 mol% CeHꢀBTC catalyst loading at 80
°C for 18 h selectively gave the antiꢀMarkovnikovꢀtype addition
product in 40% yield (entry 1, Table 1).23 Increasing catalyst
loading to 0.5 mol% afforded the addition product in 79% yield
(entry 2, Table 1). Hydroboration proceeded for several kinds of
alkenes that we tested. Hydroboration of 4ꢀfluorostyrene gave the
corresponding addition product in high yield (entry 3, Table 1).
Aliphatic alkenes, such as allylbenzene and 1ꢀoctene, were also
used in hydroboration (entries 4 and 5, Table 1). αꢀmethyl styꢀ
rene, a disubstituted alkene, was also a good substrate (entry 6,
Table 1).
4
80
50
12
6c
12
41
a1H NMR yield was determined by CH3NO2 as an internal standꢀ
c
ard. b18 h. 100 °C.
Table 1. CeHꢀBTC Catalyzed Hydroboration of Alkenes
We conducted several experiments to demonstrate the heteroꢀ
geneity of CeHꢀBTC. First, we showed that the PXRD of CeHꢀ
BTC recovered from hydroboration of pyridines and alkenes reꢀ
mained the same as that of freshly prepared CeHꢀBTC. Second,
we used ICPꢀMS to show that the amounts of Ce leaching into the
supernatant during the hydroboration of pyridine and styrene and
the hydrophosphination of 1ꢀoctene were less than 0.6%, 0.75%,
and 0.03%, respectively. Finally, CeHꢀBTC could be recovered
Entry
1
Substrate
Catalyst Loadꢀ Yield (%)a
ing (mol% Ce)
0.1
40
3
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
and reused 1 to 7 times without any loss of activity in each of the
Cambridge, 2013.
1
2
3
4
5
6
7
8
above reactions (Schemes S1ꢀ3, SI).
(9) Zhao, Y.; Li, K.; Li, J. Z. Naturforsch. 2010, 65b, 976ꢀ998.
In summary, we synthesized the new CeꢀBTC MOF with a
(10) (a) Wang, Z.; Cohen, S. M. Chem. Soc. Rev. 2009, 38, 1315.
(b) Tanabe, K. K.; Cohen, S. M. Chem. Soc. Rev. 2011, 40, 498.
(11) (a) Manna, K.; Ji, P.; Greene, F. X.; Lin, W. J. Am. Chem.
Soc. 2016, 138, 7488. (b) Klet, R. C.; Tussupbayev, S.; Borycz,
J.; Gallagher, J. R.; Stalzer, M. M.; Miller, J. T.; Gagliardi, L.;
Hupp, J. T.; Marks, T. J.; Cramer, C. J.; Delferro, M.; Farha, O.
K. J. Am. Chem. Soc. 2015, 137, 15680. (c) Comito, R. J.;
Fritzsching, K. J.; Sundell, B. J.; SchmidtꢀRohr, K.; Dinca, M. J.
Am. Chem. Soc. 2016, 138, 10232.
(12) (a) Zhang, T.; Manna, K.; Lin, W. J. Am. Chem. Soc. 2016,
138, 3241. (b) Thacker, N. C.; Lin, Z.; Zhang, T.; Gilhula, J. C.;
Abney, C. W.; Lin, W. J. Am. Chem. Soc. 2016, 138, 3501. (c)
Falkowski, J. M.; Sawano, T.; Zhang, T.; Tsun, G.; Chen, Y.;
Lockard, J. V.; Lin, W. J. Am. Chem. Soc. 2014, 136, 5213. (d)
Manna, K.; Zhang, T.; Carboni, M.; Abney, C. W.; Lin, W. J. Am.
Chem. Soc. 2014, 136, 13182.
(13) (a) Genna, D. T.; WongꢀFoy, A. G.; Matzger, A. J.; Sanford,
M. S. J. Am. Chem. Soc. 2013, 135, 10586. (b) Choi, K. M.; Na,
K.; Somorjai, G. A.; Yaghi, O. M. J. Am. Chem. Soc. 2015, 137,
7810. (c) Wang, C.; deKrafft, K. E.; Lin, W. B. J. Am. Chem. Soc.
2012, 134, 7211.
(14) Jiang, J.; Yaghi, O. M. Chem. Rev. 2015, 115, 6966ꢀ6997
(15) (a) Phan, A.; Czaja, A. U.; Gándara, F.; Knobler, C. B.;
Yaghi, O. M. Inorg. Chem. 2011, 50, 7388. (b) Xiao, D. J.; Bloch,
E. D.; Mason, J. A.; Queen, W. L.; Hudson, M. R.; Planas, N.;
Borycz, J.; Dzubak, A. L.; Verma, P.; Lee, K.; Bonino, F.;
Crocellá, V.; Yano, J.; Bordiga, S.; Truhlar, D. G.; Gagliardi, L.;
Brown, C. M.; Long, J. R. Nat. Chem. 2014, 6, 590. (c) Metzger,
E. D.; Brozek, C. K.; Comito, R. J.; Dincă, M. ACS Cent. Sci.
2016, 2, 148.
(16) Lammert, M.; Wharmby, M. T.; Smolders, S.; Bueken, B.;
Lieb, A.; Lomachenko, K. A.; De Vos, D.; Stock, N. Chem.
Commun. 2015, 51, 12578.
(17) Furukawa, H.; Gándara, F.; Zhang, Y.ꢀB.; Jiang, J.; Queen,
W. L.; Hudson, M. R.; Yaghi, O. M. J. Am. Chem. Soc. 2014,
136, 4369.
(18) Behrsing, T.; Bond, A. M.; Deacon, G. B.; Forsyth, C. M.;
Forsyth, M.; Kamble, K. J.; Skelton, B. W.; White, A. H. Inorg
Chim Acta 2003, 352, 229.
(19) (a) Bull, J. A.; Mousseau, J. J.; Pelletier, G.; Charette, A. B.
Chem. Rev. 2012, 112, 2642. (b) Lavilla, R. J. Chem. Soc., Perkin
Trans. 1 2002, 1141. (c) Stout, D. M.; Meyers, A. Chem. Rev.
1982, 82, 223.
CeIV
(ꢀ
3ꢀO)4(
ꢀ
3ꢀOH)4(OH)6(OH2)6 SBU and transformed the
6
SBU into a [CeIII
(
ꢀ3ꢀO)4(
ꢀ
3ꢀOLi)4(H)6(THF)6]6+ node, which act
6
as an active catalyst for the selective hydroboration of pyridine
and alkenes and hydrophosphination of alkenes. The CeHꢀBTC
catalyst displayed lower steric hindrance and electron density than
other lanthanide catalysts, which likely accounts for the unique
1,4ꢀ regioꢀselectivity for the hydroboration of pyridine. MOF
nodes thus have great potential for transformation into singleꢀsite
solid catalysts without homogeneous counterparts for sustainable
chemical synthesis.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ASSOCIATED CONTENT
Supporting Information
General experimental section; synthesis and characterization of
CeꢀBTC, CeOHꢀBTC, and CeHꢀBTC; MOF catalyzed hydroboraꢀ
tion and hydrophosphination. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
wenbinlin@uchicago.edu
Author Contributions
†These authors contributed equally.
ACKNOWLEDGMENT
This work was supported by NSF (CHEꢀ1464941). We thank G.
Lan and M. Piechowicz for experimental help. XAS analysis was
performed at Beamline 10BMꢀB, supported by the Materials
Research Collaborative Access Team (MRCAT) and Beamline 9ꢀ
BM, Advanced Photon Source (APS), Argonne National
Laboratory (ANL). Use of the Advanced Photon Source, an Ofꢀ
fice of Science User Facility operated for the U.S. DOE Office of
Science by ANL, was supported by the U.S. DOE under Contract
No. DEꢀAC02ꢀ06CH11357.
REFERENCES
(1) (a) Gromada, J.; Carpentier, J.ꢀF.; Mortreux, A. Coord. Chem.
Rev. 2004, 248, 397. (b) Hou, Z.; Wakatsuki, Y. Coord. Chem.
Rev. 2002, 231, 1. (c) Kobayashi, S. Lanthanides: chemistry and
use in organic synthesis; Springer: New York, 1999.
(2) (a) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada,
M. Chem. Rev. 2008, 108, 3795. (b) Hong, S.; Marks, T. J. Acc.
Chem. Res. 2004, 37, 673. (c) Molander, G. A.; Romero, J. A. C.
Chem. Rev. 2002, 102, 2161.
(3) Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957.
(4) Kobayashi, S.; Sugiura, M.; Kitagawa, H.; Lam, W. W.ꢀL.
Chem. Rev. 2002, 102, 2227.
(5) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187.
(6) (a) Sridharan, V.; Menéndez, J. C. Chem. Rev. 2010, 110,
3805. (b) Piro, N. A.; Robinson, J. R.; Walsh, P. J.; Schelter, E. J.
Coord. Chem. Rev. 2014, 260, 21. (c) Nair, V.; Deepthi, A. Chem.
Rev. 2007, 107, 1862. (d) Nair, V.; Balagopal, L.; Rajan, R.;
Mathew, J. Acc. Chem. Res. 2004, 37, 21. (d) Vivier, L.; Duprez,
D. ChemSusChem 2010, 3, 654.
(20) Edraki, N.; Mehdipour, A. R.; Khoshneviszadeh, M.; Miri,
R. Drug Discov. Today 2009, 14, 1058.
(21) (a) Zheng, C.; You, S.ꢀL. Chem. Soc. Rev. 2012, 41, 2498.
(b) Rueping, M.; Dufour, J.; Schoepke, F. R. Green Chem. 2011,
13, 1084. (c) Ouellet, S. G.; Walji, A. M.; Macmillan, D. W. Acc.
Chem. Res. 2007, 40, 1327.
(22) (a) Fan, X.; Zheng, J.; Li, Z. H.; Wang, H. J. Am. Chem. Soc.
2015, 137, 4916. (b) Kaithal, A.; Chatterjee, B.; Gunanathan, C.
Org. Lett. 2016, 18, 3402.
(23) (a) Intemann, J.; Lutz, M.; Harder, S. Organometallics 2014,
33, 5722. (b) Dudnik, A. S.; Weidner, V. L.; Motta, A.; Delferro,
M.; Marks, T. J. Nat. Chem. 2014, 6, 1100. (c) Oshima, K.;
Ohmura, T.; Suginome, M. J. Am. Chem. Soc. 2012, 134, 3699.
(d) Arrowsmith, M.; Hill, M. S.; Hadlington, T.; KociokꢀKöhn,
G.; Weetman, C. Organometallics 2011, 30, 5556.
(24) The reaction did not proceed with CeꢀBTC or without cataꢀ
lyst.
(25) (a) Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957. (b)
Burgess, K.; Ohlmeyer, M. J. Chem. Rev. 1991, 91, 1179. (c)
Zhang, L.; Peng, D.; Leng, X.; Huang, Z. Angew. Chem., Int. Ed.
2013, 52, 3676
(7) (a) Jeske, G.; Schock, L. E.; Swepston, P. N.; Schumann, H.;
Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8103. (b) Fendrick, C.
M.; Mintz, E. A.; Schertz, L. D.; Marks, T. J. Organometallics
1984, 3, 819.
(8) Llabres i Xamena, F.; Gascon, J. Metal Organic Frameworks
as Heterogeneous Catalysts; The Royal Society of Chemistry:
(26) (a) Koshti, V.; Gaikwad, S.; Chikkali, S. H. Coord. Chem.
Rev. 2014, 265, 52. (b) Delacroix, O.; Gaumont, A. Current Org.
4
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
Chem. 2005, 9, 1851.
Chem. Soc. 2014, 136, 9240. (b) LeyvaꢀPérez, A.; VidalꢀMoya, J.
1
2
3
(27) Quin, L. D. A guide to organophosphorus chemistry; John
Wiley & Sons, New York, 2000.
(28) (a) Ghebreab, M. B.; Bange, C. A.; Waterman, R. J. Am.
A.; CabreroꢀAntonino, J. R.; AlꢀDeyab, S. S.; AlꢀResayes, S. I.;
Corma, A. J. Organomet. Chem. 2011, 696, 362.
TOC:
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
5
ACS Paragon Plus Environment