Cofacial dicobalt complex of a binucleating hexacarboxamide cryptand ligand

Article abstract of DOI:10.1021/ic100395a

A hexacarboxamide cryptand featuring appended polyether moieties is used as a binucleating ligand for two Co^II centers, marking the first time cryptands have been used as hexaanionic N donors for metal coordination. A synthesis for the hexacarboxamide cryptand, culminating in a 23% yield high-dilution step and proceeding in 8% overall yield, is reported. The ligand is metalated using cobalt(II) acetate, and a solid-state structure is presented, revealing an intermetallic void over 6.4 A in length. The reactivity of this new type of cryptate is also probed; treatment of the dicobalt cryptate with potassium cyanide at elevated temperature results in a bridging cyanide complex.

Full text of DOI:10.1021/ic100395a

Inorg. Chem. 2010, 49, 3697–3699 3697
DOI: 10.1021/ic100395a
Cofacial Dicobalt Complex of a Binucleating Hexacarboxamide Cryptand Ligand
€
Glen E. Alliger, Peter Muller, Christopher C. Cummins,* and Daniel G. Nocera*
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge,
Massachusetts 02139
Received February 26, 2010
A hexacarboxamide cryptand featuring appended polyether moie-
ties is used as a binucleating ligand for two CoII centers, marking
the first time cryptands have been used as hexaanionic N donors
for metal coordination. A synthesis for the hexacarboxamide
cryptand, culminating in a 23% yield high-dilution step and proceeding
in 8% overall yield, is reported. The ligand is metalated using
cobalt(II) acetate, and a solid-state structure is presented, reveal-
Notably, whereas cryptands bearing carboxamide functiona-
lities have been used to bind anions,10 they have not yet been
employed as anionic ligands in transition-metal chemistry,
despite the well-documented chemistry as trianions of their
monometallic TREN-based parentage.4 With the foregoing
precedent in mind, we sought to develop the coordination
chemistry of hexacarboxamido cryptands, with an emphasis
on employing them in hexadeprotonated form as binucleat-
ing ligands. Herein we report the first such complex, obtained
as a cofacial dicobalt(II) species lacking any axial bridging
ligand, together with information on cyanide insertion into
this system’s central cavity.
˚
ing an intermetallic void over 6.4 A in length. The reactivity of this
new type of cryptate is also probed; treatment of the dicobalt
cryptate with potassium cyanide at elevated temperature results in
a bridging cyanide complex.
The target ligand was furnished by following the protocol
delineated in Scheme 1. Iodination of dimethyl isophthalate
was achieved using iodine and sodium periodate in neat
sulfuric acid,11 an economical alternative to the more com-
monly employed N-iodosuccinimide used in the iodination of
deactivated arenes.12 Installation of the dipropoxyphenoxyl
substituent was achieved through the use of a copper(I)
triflate-catalyzed coupling.13 Attachment of the polyether
moiety to the ligand significantly enhances its solubility.
Saponification of the ester residues and subsequent activa-
tion with N-hydroxysuccinimide and N-[3-(dimethylamino)-
propyl]-N0-ethylcarbodiimide hydrochloride (EDAC) yielded
disuccinimido ester 1. Treatment of 1 with 0.67 equiv of
TREN under high-dilution conditions resulted in the ligand
H6L (2) in 8% overall yield. The final step in this synthesis
proceeds in 23% yield, engendering a useful methodology on
the laboratory scale; multigram quantities of the ligand can
be isolated routinely.
Originally conceived as a three-dimensional extension of
the contemporary crown ethers,1,2 cryptands have been used
in a wide variety of synthetic capacities, although they are
more classically known for their alkali cation sequestration
abilities.3 Their ability to bind a transition metal is associated
with the proclivity of tris(2-aminoethyl)amine (TREN) to
envelop metals within its trigonal-pyramidal cleft.4 The
discovery that the treatment of 3 equiv of an aryl dialdehyde
with 2 equiv of TREN to furnish hexaiminocryptands in
good yield,5 without the need for high-dilution conditions,6,7
facilitated the extension to a bimetallic motif: hexaimino-
cryptands, as well as their reduced octaaza counterparts, are
competent binucleating ligands for transition metals8 and for
the formation of cascade complexes, wherein a small mole-
cule or anion bridges the metal centers.9 To date, these
ligands have been predominantly utilized as neutral donors.
Double cobalt(II) insertion into and hexadeprotonation of
the cryptand ligand were accomplishedasshownin Scheme 2,
reaction a. Treatment of a slurry of 2 and 2 equiv of cobalt(II)
acetate with 6.1 equiv of potassium hexamethyldisilazide in
N,N-dimethylformamide (DMF) resulted in the formation of
K2(DMF)6Co2L (3) in 60% yield with concomitant precipi-
tation of potassium acetate. The desired product precipitates
directly from the crude DMF reaction solution upon the
*To whom correspondence should be addressed. E-mail: ccummins@
mit.edu (C.C.C.), nocera@mit.edu (D.G.N.).
(1) Dietrich, B.; Lehn, J.-M.; Sauvage, J. P. Tetrahedron Lett. 1969, 10,
2885–2888.
(2) Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 7017–7036.
(3) Dietrich, B.; Lehn, J.-M.; Sauvage, J. P. Tetrahedron Lett. 1969, 10,
2889–2892.
(4) (a) Cummins, C. C.; Lee, J.; Schrock, R. R.; Davis, W. D. Angew.
Chem., Int. Ed. 1992, 31, 1501–1503. (b) Schrock, R. R. Acc. Chem. Res. 1997,
30, 9–16.
(10) Bowman-James, K. Acc. Chem. Res. 2005, 38, 671–678.
(11) Kraszkiewicz, L.; Sosnowski, M.; Skulski, L. Synthesis 2006, 1195–
1199.
(12) Prakash, G. K. S.; Mathew, T.; Hoole, D.; Esteves, P. M.; Wang, Q.;
Rasul, G.; Olah, G. A. J. Am. Chem. Soc. 2004, 126, 15570–15776.
(13) Marcoux, J.-F.; Doye, S.; Buchwald, S. L. J. Am. Chem. Soc. 1997,
119, 10539–10540.
(5) MacDowell, D.; Nelson, J. Tetrahedron Lett. 1988, 29, 385–386.
(6) Dietrich, B. Cryptands. In Comprehensive Supramolecular Chemistry;
Gokel, G. W., Ed.; Elsevier Science: New York, 1996; Vol. 1, pp 153-211.
(7) Krakowiak, K. E.; Bradshaw, J. S. Isr. J. Chem. 1992, 32, 3–13.
(8) Drew, M. G. B.; MacDowell, D.; Nelson, J. Polyhedron 1988, 7, 2229–
2232.
(9) Lehn, J.-M. Pure Appl. Chem. 1977, 6, 857–870.
r
2010 American Chemical Society
Published on Web 03/25/2010
pubs.acs.org/IC

3698 Inorganic Chemistry, Vol. 49, No. 8, 2010
Scheme 1. Synthesis of Ligand 2a
Alliger et al.
Figure 1. PLATON rendering of 3 with thermal ellipsoids drawn at
50% probability. Solvent molecules of crystallization, Kþ counterions,
dipropoxyphenoxyl groups, and H atoms are omitted for clarity.
a (a) NaIO4, I2, H2SO4, 30 °C, 61%. (b) 3,5-Dipropoxyphenol,
anionic TREN pockets [sum of Neq-Co-Neq(avg) =
358.2°] with trigonal-monopyramidal geometry. No residual
electron density was observed in the void between the Co
centers, ruling out the presence of a second axial ligand. The
(CuOTf )2 C6H6, CsCO3, molecular sieves, THF, 100 °C, 61%. (c)
3
Aqueous NaOH, MeOH, 20 °C, 99%. (d) NHS, EDAC, CH2Cl2, 92%
(Su = succinimido). (e) 0.67 equiv of TREN, CH2Cl2, 23%.
˚
distance between the metal centers is 6.4078 A (avg).
Scheme 2. Synthesis of μ-Cyanide Complex 5 from Ligand 2a
The structure of 3 reveals that Kþ ions bridge the dicobalt
cryptate units, resulting in an extended three-dimensional
structure. This is in analogy to protonated cryptands, which
may form an extended three-dimensional structure by hydro-
gen bonding to interstitial anions.15 Perhaps because of this
extended structure, 3 is soluble only in highly polar solvents
such as DMF and DMSO. Treatment of a slurry of 3 in
tetrahydrofuran (THF) with 2 equiv of 18-crown-6, however,
results in a homogeneous solution. The Kþ ions in [K(18-
crown-6)]2Co2L (4) are sequestered, thus interrupting the
extended structure. Accordingly, compound 4 is soluble in
less polar solvents such as THF, methylene chloride, chloro-
form, and acetonitrile.
a (a) 2 equiv of Co(OAc)2, 6.1 equiv of KN(SiMe3)2, DMF, 2 h, -61
°C to rt, -4 KOAc. (b) 2 equiv of 18-crown-6, THF, rt, 1 h. (c) 18-crown-
6, KCN, DMF, 75 °C, 48 h.
While a VOID analysis performed by PLATON16 suggests
that there is not enough space in the intermetallic cleft to
accommodate ligands even as small as a water molecule,
treatment of 4 with an excess of potassium cyanide and 18-
crown-6 in DMF at 75 °C for 2 days elicits a color change
from turquoise to vibrant pink, indicative of cyanide bind-
ing,17 as well as the appearance of a weak band at 2129 cm-1
in the IR spectrum (see the Supporting Information for UV/
vis and IR spectra). The weakness of stretches arising from
cyanide ligands bridging metal centers in trigonal-bipyrami-
dal geometries is precedented.18 1H NMR spectra of the new
species indicatea smooth conversion toa paramagneticentity
( μeff = 6.21 μB)14 that no longer possesses reflective symme-
try through a mirror plane perpendicular to the metal-metal
vector, as observed for complexes 3 and 4. Crystals of cyanide
adduct[K(18-crown-6)]3Co( μ-CN)CoL (5) were grown from
a THF solution layered with pentane; the ensuing structure is
depicted in Figure 2. It is an affirmative illustration of
cryptand internal cavity accessibility that the cyanide anion
undergoes a reaction to penetrate the barrier defined by the
xylylene spacer arms of 4 and to take up residence there as an
axial bridging ligand; that water does not bind may speak to
addition of ether. 1H NMR resonances in the spectrum of 3
are paramagnetically broadened and shifted, as expected for
a complex incorporating a pair of weakly coupled d7 metal
ions (a solution-phase magnetic susceptibility measurement14
yielded μeff = 6.52 μB). Shifts corresponding to phenylene
and propyl protons from the propoxyphenoxyl moiety are
observed between δ 2.5 and 11.2. Six resonances correspond-
ing to the phenylene spacer aryl and TREN methylene
protons are observed between δ -60 and þ70. Four reso-
nances are observed for the TREN methylene residues,
suggesting that these protons are diastereotopic for the
compound in solution, an indication of rigidity of the C3h-
symmetric molecular framework on the NMR time scale.
NMR studies also reveal the stability of 3 to water: overnight
agitation in the presence of 14 equiv of water in a deuterated
dimethyl sulfoxide (DMSO-d6) solution indicated no decom-
position; heating of this mixture at 75 °C for 2 days resultedin
no change in the NMR spectrum.
Crystals suitable for X-ray diffraction studies were ob-
tained by vapor diffusion of ether into a DMF solution of 3.
Structural analysis of 3 reveals that two crystallographically
independent but chemically equivalent units compose the
asymmetric unit. The core of one of these units can be seen in
Figure 1, with the solubilizing polyether groups omitted for
clarity. This view clearly shows the metal centers residing in
(15) Chin, A.; Edgar, M.; Harding, C. J.; McKee, V.; Nelson, J. Dalton
Trans. 2009, 6315–6326.
(16) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7–13.
(17) Jones, M. B.; MacBeth, C. E. Inorg. Chem. 2007, 46, 8117–8119.
(18) (a) Duggan, D. M.; Jungst, R. G.; Mann, K. R.; Stucky, G. D.;
Hendrickson, D. N. J. Am. Chem. Soc. 1974, 96, 3443–3450. (b) Scott, M. J.;
Lee, S. C.; Holm, R. H. Inorg. Chem. 1994, 33, 4651–4662.
(14) (a) Evans, D. F. J. Chem. Soc. 1959, 2003–2005. (b) Sur, S. K. J. Magn.
Reson. 1989, 169–173.

Communication
Inorganic Chemistry, Vol. 49, No. 8, 2010 3699
Figure 3. Cyclic voltammagrams of 3 (left) and 5 (right). Voltamma-
grams are referenced to ferrocene/ferrocenium.
Modeling the cyanide ligand as positionally disordered in
an end-over-end fashion yielded the best crystallographic
model. The free variable associated with this aspect of the
model refined to a value of 0.63(3), indicating that, in 63% of
the crystalline sample, C3 is bound to Co2. The observed
albeit moderate preference for C3 binding to Co2 is coin-
cident with the coordination of all three Kþ counterions to
this pole of the cryptand complex.
The present work provides an efficient, reproducible hexa-
carboxamide cryptand ligand synthesis that is potentially
variable at the xylylene spacer substituent, here chosen as
3,5-dipropoxyphenoxy for solubility purposes. In addition, a
convenient protocol has been established for the concomitant
hexadeprotonation of and double divalent metal-ion inser-
tion into the new ligand framework. Structural data have
been obtained both for the empty dicobalt(II) derivative and
for its cyanide inclusion complex, setting the stage for an
exploration of the small-molecule chemistry of such systems
employing metal ions transiting the 3d series.
Figure 2. PLATON rendering of 5 with thermal ellipsoids drawn at
50% probability. Crown ethers, solvents of crystallization, dipropoxy-
phenoxyl groups, and H atoms are omitted for clarity. One phenylene
spacer has been grayed for ease of viewing.
the ability of the spacers to protect against the coordination
of weaker ligands. Cyanide insertion between the Co centers
has a profound effect on the geometry of the supporting
bimetallic scaffold. The Co metal centers are pulled from
their respective TREN binding pockets [3, Co1;Co2 =
˚
˚
6.4078 A (avg); 5, Co1;Co2 = 5.3263(9) A] to a sufficient
extent that the primary coordination sphere of the metal
P
is best described as tetrahedral [
= 340.76(23)°;
Co1(eq)
P
= 343.07(24)°]. The distance between the Co
Co2(eq)
Acknowledgment. The compounds were discovered un-
der the sole sponsorship of Eni SpA under the Eni-MIT
Alliance Solar Frontiers Program. Characterization work
was performed under grants from the National Science
Foundation (Grants CHE-0533150 and CHE-0802907).
centers and their respective apical N atoms increases from
˚
˚
an average of 2.142(5) A in 3 to 2.494(3) A (Co1-N1)
and 2.425(3) A (Co2-N2) in 5. Cyanide coordination also
˚
affects the electrochemical properties of the cobalt complex
(Figure 3). While 3 exhibits an irreversible oxidation wave
at 1090 mV, cyanide complex 5 exhibits a cathodic wave
at -1200 mV and an anodic wave at -225 mV (voltages
quoted vs Fc/Fcþ); these features are independent of one
another.
Supporting Information Available: Experimental procedures
and characterization data for all new compounds, as well as
crystallographic details for compounds 3 and 5. This material is
available free of charge via the Internet at http://pubs.acs.org.