Iodosylbenzene and iodylbenzene adducts of cerium(IV) complexes bearing chelating oxygen ligands

Article abstract of DOI:10.1039/c6dt00267f

Reactions of [Ce^IV(L_OEt)₂Cl₂] (L_OEt^- = [Co(η⁵-C₅H₅){P(O)(OEt)₂}₃]^-) and [CeIV2(μ-O){N(Prⁱ₂PO)₂}₄Cl₂] with PhIO afford the λ₃-iodane complexes [Ce^IV(L_OEt)₂{OI(Cl)Ph}₂] and [CeIV2{N(Prⁱ₂PO)₂}₃{OI(Cl)Ph}], respectively, whereas that between [Ce^IV(L_OEt)₂Cl₂] and PhIO₂ or excess PhIO yields the λ₅-iodane adduct [Ce^IV(L_OEt)₂{OI(O)ClPh}₂]. The crystal structures of the Ce^IV λ₃- and λ₅-iodane complexes have been determined and their oxo transfer reactivities have been investigated.

Full text of DOI:10.1039/c6dt00267f

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Iodosylbenzene and Iodylbenzene Adducts of Cerium(IV)
†
Complexes Bearing Chelating Oxygen Ligands
Received 00th January 20xx,
Accepted 00th January 20xx
Ka-Chun Au-Yeung,a Yat-Ming So,a Guo-Cang Wang,a Herman H.-Y. Sung ,a Ian D. Williamsa and
Wa-Hung Leung*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
-
Reactions of [CeIV(LOEt)2Cl2] (LOEt = [Co(η5-C5H5){P(O)(OEt)2}3]-) and pyridyl)phenyl, sPhIO = 2-tert-butylsulfonyliodosylbenzene)6
[CeIV2(ꢀ-O){N(Pri2PO)2}4Cl2] with PhIO afford the λ3-iodane have been isolated from the reactions of PhIO with the
complexes
[CeIV(LOEt)2{OI(Cl)Ph}2]
and corresponding metal complexes and characterised by X-ray
[CeIV2{N(Pri2PO)2}3{OI(Cl)Ph}], respectively whereas that between diffraction. Also, FeIV oxo complexes with porphyrin cation
[CeIV(LOEt)2Cl2] and PhIO2 or excess PhIO yields the λ5-iodane radicals were found to be in equilibrium with Fe-OIAr species
adduct [CeIV(LOEt)2{OI(O)ClPh}2]. The crystal structures of the CeIV in the presence of iodosylarenes (ArIO).7 A recent study
λ3- and λ5-iodane complexes have been determined and their oxo revealed that instead of FeIV oxo species, the iodosylarene
transfer reactivity has been investigated.
adducts [Fe(13-TMC)(ArIO)]+ (13-TMC = 1,4,7,10-tetramethyl-
1,4,7,10-tetraazacyclotridecane; Ar = substituted phenyl) are
the active oxidants for the [Fe(13-TMC)]-catalysed epoxidation
of alkenes with ArIO.8
Iodosylbenzene (PhIO) and related hypervalent iodine
compounds have attracted considerable attention due to their
widespread applications in organic synthesis.1 PhIO has been
used as an oxygen atom transfer reagent for generation of
high-valent metal-oxo species that are reactive intermediates
in metal-mediated oxygenations.2 Previous studies have shown
that the metal-PhIO adduct formation plays a role in metal-
catalysed oxidations using PhIO as the terminal oxidant. The
Although PhIO adducts of transition-metal complexes are
well documented, to our knowledge, analogous complexes of
lanthanide elements have not been reported. Also, metal
complexes with
known. Compared with 2-iodoxybenzoic acid (IBX) and related
5-iodane compounds, the use of PhIO2 in organic oxidations
λ5-iodane ligands such as PhIO2 are not
λ
has received less attention due, in part, to its explosive nature
and poor solubility in organic solvents.1a We recently
synthesised CeIV permanganate complexes supported by the
chelating oxygen ligands [Co(η5-C5H5){P(O)(OEt)2}3]- (LOEt-) and
[N(Pri2PO)2]- (Scheme 1), [CeIV(LOEt)2(MnVIIO4)2]9 and
[CeIV{N(Pri2PO)2}3(MnVIIO4)]2,10 that can oxidise C-H bonds of
alkylbenzenes at room temperature more efficiently than
KMnO4 does. This result indicates the ability of the
electrophilic CeIV centre in stabilising reactive oxo species, and
prompted us to synthesise PhIO adducts of CeIV complexes
bearing chelating oxygen ligands. Herein, we report the
isolation and crystal structures of the first lanthanide
λ
3-iodane adducts trans-[MnIV(por){OI(OAc)Ph}2] (por2-
=
3
porphyrin
dianion,
OAc-
=
acetate)
trans-
[MnIV(salen){OI(Cl)Ar}2] [salen2- = quadridentate Schiff base
dianion; Ar = Ph, mesityl (mes)],4 [FeIII(tpena)(OIPh)]+ (tpena- =
N,N,N’-tris(2-pyridylmethyl)ethylendiamine-N’-acetate)5 and
[RhIIICp*(ppy)(sPhIO)]+ (Cp*
=
η5-C5Me5, ppy
=
2-(2-
compounds containing
transfer reactivity.
λ
3- and λ5-iodane ligands, and their oxo
Pri
Pri
P
P
O
EtO
EtO
Co
P
OEt
OEt
=
N
P
P
O
O
=
EtO
OEt
-
O
O
O
O
O
O
O
Pri
Pri
LOEt
[N(Pri2PO)2]-
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Scheme 1. Structures of the chelating oxygen ligands [Co(η5-C5H5){P(O)(OEt)2}3]-
Fig. 1. Molecular structure of
1
. Hydrogen atoms are omitted for clarity. Thermal
(LOEt-) (left) and [N(Pri2PO)2]- (right).
ellipsoids are drawn at 30% probability level. Selected bond lengths (Å) and angles
(o): Ce-O(I) 2.262(5) and 2.202(5), I-O 1.918(4), 1.950(4), I-Cl 2.819(18) and 2.718(2); Ce-
O-I 122.1(2) and 129.4(2).
Cl
O
I
O
Ph
O
2 PhIO
O
[Ce(LOEt)2Cl2]
Ce
O
O
O
O
I
Ph
Cl
1
O
O
O
PhIO
Ce
O
O
[Ce2(ꢀ-O){N(Pri2PO)2}4Cl2]
Ph
Cl
O
I
O
2
+ other Ce product(s)
Scheme 2. Syntheses of the CeIV PhIO complexes
1 and 2.
The treatment of [CeIV(LOEt)2Cl2] with 2 equivalents of PhIO
in MeCN at room temperature resulted in the formation of the
Fig. 2. Molecular structure of 2. Hydrogen atoms are omitted for clarity. Thermal
ellipsoids are drawn at 30% probability level. Selected bond lengths (Å) and angle (o):
bis(PhIO) adduct [CeIV(LOEt)2{OI(Cl)Ph}2] (
insertion of PhIO into the Ce-Cl bonds (Scheme 2).
to synthesise the mono-PhIO adduct by reacting [CeIV(LOEt)2Cl2]
with one equivalent of PhIO was not successful; only was
1), apparently through
Ce-O(I) 2.171(2), I-O 1.966(2), I-Cl 2.6711(10); Ce-O-I 124.92(12).
§
An attempt
1
Although CeIV iodate and periodate are well documented12
isolated in low yield. No reaction was found between PhIO and
[LnIII(LOEt)2(H2O)2Cl] (Ln = La, Sm),11 indicating that the PhIO
adduct formation is a unique reaction for the tetravalent
lanthanide complex. A preliminary study showed that PhIO
also forms adducts with other CeIV-LOEt complexes such as
and have been used in organic oxidations,13
1
and
3-iodane compounds that have been
characterised by X-ray diffraction. The crystal structures of
and are shown in Figs. 1 and 2, respectively. The geometry
around Ce in is pseudo dodecahedral, whereas that for can
be described as mono-capped octahedral. The Ce-O(P)
distances in and are normal by comparison with those in
reported CeIV complexes with LOEt and [N(Pri2PO)2]- ligands.9,10
The Ce-O-I units in and are bent with average bond angles
of 125.8 and 124.92(12)o, respectively. The Ce-O(I) distances in
[2.265(5) and 2.202(5) Å] and [2.171(2) Å] are shorter than
2 are the
first molecular CeIV
λ
1
2
[CeIV(LOEt)2X2]
[CeIV{N(Pri2PO)2}3Cl] did not react with PhIO under the same
conditions, [CeIV{N(Pri2PO)2}3{OI(Cl)Ph}] (
) was isolated from
[CeIV -O){N(Pri2PO)2}4Cl2] and PhIO, presumably via
dinuclear intermediate, [Ce2(
-O){N(Pri2PO)2}4{OI(Cl)Ph}2], that
undergoes ligand re-distribution to give the tris(chelate)
product . The fate of the -oxo ligand in the dinuclear
(X-
=
tosylate,
triflate).
Although
1
2
1
2
2
-
(
ꢀ
a
2
1
2
ꢀ
1
2
2
ꢀ
those in the layered cerium iodates Ce2(IO3)6(OHx) (x = 0 or
0.44) [2.323(3) – 2.557(6) Å]12 and consistent with Ce-O single
intermediate is not clear, and the Ce-containing by-product,
possibly a CeIV complex with one [N(Pri2PO)2]- ligand, has not
bonds. As expected, the geometry around the IIII centres in
1
been isolated. Both complexes 1 and 2 are diamagnetic (Evans
method, chloroform) and exhibit sharp 1H NMR signals,
consistent with the CeIV formulation. The observed 31P NMR
and
Å] and
[Mn(salen){OI(Cl)mes}2] [1.888(3) and 1.853(4) Å].4
2
is T-shaped. The I-O distances in
1 [1.918(4) and 1.950(4)
2
[1.966(2) Å] are longer than those in trans-
resonant signals at
δ 117.4 and 49.5 ppm for 1 and 2,
-
respectively, are typical for CeIV complexes with LOEt and
The oxo transfer reactivity of
(Scheme 3). The reaction of
1
1
has been investigated
with PPh3 afforded
[N(Pri2PO)2]-.9,10
approximately two equivalents of OPPh3 (eq 1, Scheme 3)
indicating that can function as a 4-electron oxidant. The Ce-
1
containing product was identified as the reported compound
[CeIV(LOEt)2Cl2] characterised by NMR spectroscopy.14 Similarly,
the reaction of 2 with PPh3 afforded one equivalent of OPPh3
along with the reported compound [CeIV{N(Pri2PO)2}3Cl] that
was characterised by NMR spectroscopy.15 Like trans-
[MnIV(salen){OI(Cl)mes}2],4
1 is capable of oxidising thioethers.
o
1 in MeCN at 40 C
The oxidation of p-tolyl methylsulfide by
afforded approximately two equivalents of p-tolyl
methylsulfoxide (with respect to Ce), with high selectivity; no
sulfone was detected (eq 2, Scheme 3). However, no reaction
was found between
1
and alkenes such as cyclooctene at 40 oC.
2 | J. Name., 2012, 00, 1-3
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disproportionation of PhIO to PhI and PhIO2 that inserted into
the Ce-Cl bonds was involved in Scheme 4. By contrast, no
reaction was found between PhIO2 and
O){N(Pri2PO)2}4Cl2]. Complex
is diamagnetic and exhibits
sharp 1H NMR signals, consistent with the CeIV formulation.
The 31P {1H} NMR spectrum of
displayed a singlet at 116.3
2 (ꢀ-
or [CeIV
2
3
3
δ
ppm. Recrystallisation from CH2Cl2/tetrahydrofuran/hexanes
afforded orange single crystals that were identified as
3
⋅
0.2H2O (Fig. 3). To our knowledge,
complex that contains a 5-iodane ligand characterised by X-
ray crystallography. The Ce-O(I) bond distances [2.265(5) and
2.338(5) Å] in are slightly longer than those in , whereas the
3⋅0.2H2O is the first metal
λ
3
1
Scheme 3. Stoichiometric oxidation of p-tolyl methylsulfide and PPh3 by 1 and 3. Yields
I-O(Ce) distances [1.885(5) and 1.853(4) Å] are shorter than
the latter. The geometry around the 4-coordinated IV centre, I2,
can be described as see-saw, whereas I1 has pseudo square
of oxidation products are based on Ce complexes used.
The CeIV complex [CeIV(LOEt)2Cl2] or
1 can catalyse the
pyramidal geometry considering the secondary
I
⋅⋅⋅
O
oxidation of p-tolyl methylsulfide with PhIO, presumably via
the intermediacy of a PhIO and/or PhIO2 (see later section)
adduct. For example, the oxidation of p-tolyl methylsulfide
with PhIO in the presence of 5 mol% of [CeIV(LOEt)2Cl2] afforded
the sulfoxide selectively in ca 99% yield (turnover number ~ 20)
(eq. 4). Under the same conditions, in the absence of the Ce
catalyst, the oxidation of p-tolyl methylsulfide with PhIO was
very slow (< 5% yield). Other LOEtCeIV complexes such as
[CeIV(LOEt)2(NO3)2] are poor catalysts for the sulfoxidation (< 5%
yield).
interaction (vide infra). The terminal I-O distances in
3
[1.793(5) and 1.794(5) Å] are comparable to those in 2-
iodoxybenzoate esters and amides [1.772(16) - 1.823(5) Å].16 A
secondary I⋅⋅⋅O interaction with a separation of 2.734(5) Å was
found between the two PhIO2 moieties in
3. Similar I⋅⋅⋅O
interactions [2.594(5)-3.074(4) Å] are commonly found in
PhIO2 and IBX derivatives in the solid state. 16-18
The bis(iodylbenzene) complex
oxidant for thioethers. However, unlike
sulfoxide, a small amount of the sulfone product was produced
from the oxidation of p-tolyl methylsulfide with (eq 3,
Scheme 3). Since was generated from the reaction of
[CeIV(LOEt)2Cl2] with excess PhIO, this raises a question as to
whether or is the active oxidant for the Ce-catalysed
3
can act as an 8-electron
1, in addition to the
3
3
1
3
sulfoxidation (eq 3). The oxidation of p-tolyl methylsulfide with
PhIO in the presence of 10 mol% of [CeIV(LOEt)2Cl2] in CD3CN
has been monitored by NMR spectroscopy (see ESI). At ca 5
min after the addition of PhIO, the signals due to [Ce(LOEt)2Cl2]
Although
1 is quite stable in dried organic solvents such as
MeCN and CH2Cl2, it decomposes slowly (> 2 h) in MeCN/water
(10:1 v/v) or pure water to give [CeIV(LOEt)2Cl2] along with
insoluble PhIO polymer. The dissociation of the PhIO moiety is
dropped while new signals assignable to
reaction proceeded (ca 10 min), the signals of both
were observed along with those of the sulfoxide product. The
catalytic oxidation completed in ca 15 min, at which all and
were converted into [CeIV(LOEt)2Cl2]. This result indicates that
both and are involved in the catalytic sulfide oxidation. A
preliminary study showed that [CeIV(LOEt)2Cl2] can also catalyse
1
appeared. As the
1
and
3
much faster upon abstraction of the chlorides from
1. Thus,
the addition of AgNO3 or NaNO3 to in MeCN resulted in
1
immediate formation of [CeIV(LOEt)2(NO3)2] and AgCl or NaCl,
along with PhIO polymer. Therefore, it appears that the
insertion and de-insertion of PhIO at the CeIV centre are facile
and reversible, apparently due to the ionic nature of the
lanthanide-ligand bonding.
1
3
1
3
the sulfide oxidation with PhIO2, involving both
active oxidants.19
1 and 3 as the
In summary, we have found that depending on
experimental conditions, the reaction of [CeIV(LOEt)2Cl2] with
PhIO led to formation of the PhIO or PhIO2 adduct. The PhIO2
adduct
3 is the first isolated metal λ5-iodane complex
characterised by X-ray diffraction. Whether analogous
iodylbenzene adducts of transition-metal complexes are
involved in transition-metal-catalysed oxidations with PhIO is
not clear. The results of this work demonstrate that the
oxidising, electrophilic CeIV ion can solubilize and activate
insoluble iodylbenzene that can find applications in oxo
transfer and organic oxidations. The study of the mechanisms
Scheme 4. Synthesis of the bis(iodylbenzene) complex 3⋅0.2H2O
Interestingly, when [CeIV(LOEt)2Cl2] was reacted with excess
PhIO (> equivalents), the bis(iodylbenzene) complex
[CeIV(LOEt)2{OI(O)(Cl)Ph}2] (
) was produced as the sole product
(Scheme 4). was also formed from the reaction of
[CeIV(LOEt)2Cl2]
with PhIO2, suggesting that the
4
3
of oxo transfer by CeIV
underway.
λ3- and λ5-iodane complexes is
§
3
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G. F. Koser, H. Tohma and Y. Kita, Top. Curr. Chem.:
The support from the Hong Kong Research Grants Council
(project numbers 602913 and 16301815) and the Hong Kong
University of Science and Technology is gratefully
acknowledged.
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Organic Synthesis, Springer, Berlin, 2003, vol. 224; (h) V. V.
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2006, 12, 130.
-
Fig. 3. Molecular structure of 3⋅0.2H2O. Hydrogen atoms, ethoxy groups in LOEt
and the co-crystallised H2O molecule are omitted for clarity. Thermal ellipsoids
are drawn at 30% probability level. Selected bond lengths (Å): Ce-O(I) 2.265(5)
and 2.338(5), I-Ot 1.793(5) and 1.794(5), I-O(Ce) 1.888(5) and 1.853(4), I(1)⋅⋅⋅O(22)
2.734(5)
8
9
S. Hong, B. Wang, M.-S. Seo, Y.-M. Lee, M.-J. Kim, H.R. Kim, T.
Ogura, R. Garcia-Serres, M. Clemancey, J.-M. Latour and W.
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Notes and references
§
Preparation of
0.024 mmol) in MeCN (5 mL) was added PhIO (11 mg, 0.05
mmol), and the mixture was stirred at room temperature until all 11 The treatment of [CeIII(LOEt)2(H2O)2Cl] with excess PhIO also
the PhIO was dissolved (ca 10 min), and the solvent was yielded
, presumably via the initial oxidation of the CeIII
removed in vacuo Recrystallisation from CH2Cl2/hexanes
complex to [CeIV(LOEt)2Cl2] that subsequently reacted with
afforded orange crystals. Yield: 36.3 mg (90%). H NMR (400
PhIO to give
MHz, CD3CN, 25 oC):
1.22 (t, = 7.2 Hz, 36H, CH3), 4.09 (m, 12 R. E. Sykora, L. Deakin, A. Mar, S. Skanthakumar, L.
1
: To a solution of [(LOEt)2CeCl2] (30 mg, 10 G.-C. Wang, H. H.-Y. Sung, F.-R Dai, W.-H., Chiu, W.-Y. Wong,
I. D. Williams and W.-H. Leung, Inorg. Chem., 2013, 52, 2556.
3
.
1
3
.
δ
J
24H, CH2), 5.06 (s, 10H, Cp), 7.69(m, 2H, Hp of Ph) 7.71 – 7.76
Soderholm and T. E. Albrecht-Schmitt, Chem. Mater., 2004,
16, 1343.
(m, 4H, Hm of Ph), 8.22 (d,
J
= 4.8 Hz, 4Ho of Ph). 31P {1H}
o
NMR (162 MHz, CD3CN, 25 C):
δ 117.4 (s). Preparation of 13 (a) W. Levason and R. D. Oldroyd, Polyhedron, 1996, 15, 409;
3
⋅
0.2H2O: To a solution of [(LOEt)2CeCl2] (30 mg, 0.024 mmol)
(b) W. P. Griffith, R. G. H. Moreea and H. I. S. Nogueira,
Polyhedron, 1996, 15, 3493. (c) H. Firouzabadi, N. Iranpoor, G.
Hajipour and J. Toofan, Synth. Commun., 1984, 14, 1033
in MeCN (5 mL) was added 2 equivalents of PhIO2 (11.8 mg,
0.047 mmol), and the mixture was stirred at room temperature
until all the PhIO2 were dissolved (ca 30 min), and the solvent 14 Y.-M. So, G.-C. Wang, Y. Li, H. H.-Y. Sung, I. D. Williams, Z. Lin
was removed in vacuo. Recrystallisation from
and W.-H. Leung, Angew. Chem. Int. Ed., 2014, 53, 1626.
CH2Cl2/tetrahydrofuran/hexanes afforded orange crystals. Yield: 15 G.-C. Wang, H. H.-Y. Sung, I. D. Williams and W.-H. Leung,
1
o
36.3 mg (87%). H NMR (400 MHz, CD3CN, 25 C):
δ
1.16 (t,
J
Inorg. Chem., 2012, 51, 3640.
= 7.2 Hz, 36H,CH3), 4.01 – 4.10 (m, 24H, CH2), 5.08 (s, 10H, 16 V. V. Zhdankin, A. Y. Koposov, D. N. Litvinov, M. J. Ferguson,
Cp), 7.57 – 7.65 (m, 6H, Ph), 8.28 (d ,
J
δ
= 6 Hz, 4H, Ph) . 31P {1H}
116.3 (s). Satisfactory
R. McDonald, T. Luu and R. R. Tykwinski, J. Org. Chem., 2005,
70, 6484.
NMR (162 MHz, CD3CN, 25oC):
analytical data were obtained for the compounds (see ESI).
17 N. W. Alcock and J. F. Sawyer, J. Chem. Soc., Dalton Trans.,
1980, 115.
1
(a) V. V. Zhdankin, Hypervalent Iodine Chemistry:
18 (a) V. V. Zhdankin, D. N. Litvinov, A. Y. Koposov, T. Luu, M. J.
Ferguson, R. McDonald and R. R. Tykwinski, Chem. Commun.,
2004, 106; (b) V. V. Zhdankin, A. Y. Koposov, B. C. Netzel, N.
V. Yashin, B. P. Rempel, M. J. Ferguson and R. R. Tykwinski,
Angew. Chem. Int. Ed., 2003, 42, 2194.
Preparation, Structure and Synthetic Applications of
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19 Under the same conditions, the Ce-catalysed oxidation of p-
tolyl methylsulfide with PhIO2 was faster than that for PhIO
(completed in ca 5 min). In addition to the sulfoxide, a small
amount of the sulfone product (ca 5%) was produced.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6DT00267F
Table of Contents Entry
Iodosylbenzene and Iodylbenzene Adducts of Cerium(IV) Complexes Bearing
Chelating Oxygen Ligands
Ka-Chun Au-Yeung, Yat-Ming So, Guo-Cang Wang, Herman H.-Y. Sung, Ian D. Williams
and Wa-Hung Leung*
Reactions of [CeIV(LOEt)2Cl2] (LOEt- = [Co(η5-C5H5){P(O)(OEt)2}3]-) with PhIO and PhIO2 afford the
[CeIV(LOEt)2{OI(Cl)Ph}2] and [CeIV(LOEt)2{OI(O)ClPh}2], respectively. The crystal structures of the
CeIV λ3- and λ5-iodane complexes have been determined and their oxo transfer reactivity has
been investigated.
Cl
O
Ph
O
O
O
Cl
Cl
I
Ph
O
O
O
I
2 PhIO2
O
O
O
2 PhIO
O
Cl
Cl
O
O
Ce
Ce
Ce
O
O
I
O
O
O
O
O
O
O
I
O
O
Ph
Ph
Cl