Multi-step and multi-component organometallic synthesis in one pot using orthogonal mechanochemical reactions

Article abstract of DOI:10.1039/c4sc01252f

We demonstrate that the mechanochemical strategies for oxidative addition and ligand substitution on organometallic centers can be mutually orthogonal, permitting the rational design of multi-component mechanochemical reaction procedures for assembling complex or solution-sensitive organometallic species from three, four or even five components in one pot. The herein established synthetic procedures represent a new level of complexity in mechanochemical reactions by milling and are the first to combine redox and ligand substitution reactions into mechanochemical strategies for either one-pot sequential ( telescoping ) or one-pot multi-component syntheses. This ability to combine mechanochemical transformations has enabled the solvent-free, room-temperature syntheses of relatively complex organometallics directly for simple zerovalent metal carbonyls as the simplest precursors. In particular, we demonstrate the efficiency of mechanochemical oxidative addition by targeting selected pentacarbonyl halides (fluoride, chloride, bromide, iodide) of rhenium(i) and manganese(i), and illustrate the potential of multi-step organometallic mechanochemistry in the syntheses of selected fac-tricarbonyl complexes of these metals.

Full text of DOI:10.1039/c4sc01252f

Chemical
Science
View Article Online
View Journal
EDGE ARTICLE
Multi-step and multi-component organometallic
synthesis in one pot using orthogonal
mechanochemical reactions†
Cite this: DOI: 10.1039/c4sc01252f
*
*
Jose G. Hernandez, Ian S. Butler and Tomislav Friscic
ˇˇ ´
´
´
We demonstrate that the mechanochemical strategies for oxidative addition and ligand substitution on
organometallic centers can be mutually orthogonal, permitting the rational design of multi-component
mechanochemical reaction procedures for assembling complex or solution-sensitive organometallic
species from three, four or even five components in one pot. The herein established synthetic
procedures represent a new level of complexity in mechanochemical reactions by milling and are the
first to combine redox and ligand substitution reactions into mechanochemical strategies for either one-
pot sequential (“telescoping”) or one-pot multi-component syntheses. This ability to combine
mechanochemical transformations has enabled the solvent-free, room-temperature syntheses of
relatively complex organometallics directly for simple zerovalent metal carbonyls as the simplest
precursors. In particular, we demonstrate the efficiency of mechanochemical oxidative addition by
targeting selected pentacarbonyl halides (fluoride, chloride, bromide, iodide) of rhenium(I) and
manganese(I), and illustrate the potential of multi-step organometallic mechanochemistry in the
syntheses of selected fac-tricarbonyl complexes of these metals.
Received 1st May 2014
Accepted 16th June 2014
DOI: 10.1039/c4sc01252f
www.rsc.org/chemicalscience
transformation of oxidative addition.11 The strategy utilized a
combination of Oxone® and a metal halide (chloride, bromide
Introduction
or iodide) to achieve stereoselective and solvent-free mechano-
chemical halogenation of piano-stool complexes of rhenium(I)
to the corresponding dihalide complexes of rhenium(III).
In principle, reliable access to a set of fundamental organ-
ometallic transformations using mechanochemistry should
enable the systematic development of cleaner, solvent-free
techniques that could parallel or even surpass the efficiency of
conventional solution-based protocols. Such development is
currently taking place in organic mechanosynthesis where the
established conventional transformations (e.g., amide
coupling,12 sulfonyl-(thio)ureas formation,13 imine condensa-
tion,14 Sonogashira,15 Suzuki16 and Huisgen17 coupling)
buttressed the development of solvent-free synthetic procedures
for making relatively complex targets, notably Leu-enkephalin18
and molecular cages.19 Despite the recently demonstrated
potential,20 however, mechanochemical syntheses still shy away
from multi-step or multi-component reaction sequences.
We now report the rational design of multi-step, as well as
multi-component organometallic synthetic procedures by
coupling the highly efficient and mutually orthogonal21 mech-
anochemical reactions of oxidative addition and ligand
exchange. In particular, we demonstrate and evaluate different
strategies to combine mechanochemical reactions for the
synthesis of increasingly complex products from metal
carbonyls as simple, least expensive and readily available
precursors. In the order of complexity and novelty, these
Mechanochemical transformations, conducted by milling or
grinding,1 have emerged as versatile and powerful alternatives
for laboratory syntheses of organic molecules,2 coordination
polymers and frameworks,3 and co-crystals.4 In these systems,
mechanochemical reactivity was shown to provide access to
noticeable reductions in the use of solvent,5 energy6 and
enhanced control of reaction stoichiometry.7 The benets of
mechanochemical synthesis have, however, hardly been
explored in the context of organometallic chemistry.8 There is
only a handful of mechanochemical organometallic trans-
formations available and multi-step synthetic procedures have
not been explored at all. Examples of mechanochemical trans-
formations involving organometallics include the work of Bra-
ga's group9 focused on the cocrystallization of ferrocene- and
cobaltocene-based units, and the work of Coville's group10 on
solvent-free ligand exchange of piano-stool complexes.
Recently, we demonstrated the rst mechanochemical, solvent-
free strategy for conducting the fundamental organometallic
Department of Chemistry and FRQNT Centre for Green Chemistry and Catalysis,
McGill University, 801 Sherbrooke St. W., Montreal H3A 0B8, Quebec, Canada.
E-mail: ian.butler@mcgill.ca; tomislav.friscic@mcgill.ca
† Electronic supplementary information (ESI) available: Experimental details,
FTIR-ATR, MS, selected PXRD and solution NMR (1H, 19F and 13C) data. CCDC
997709–997711. For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c4sc01252f
This journal is © The Royal Society of Chemistry 2014
Chem. Sci.

View Article Online
Chemical Science
Edge Article
strategies include: stepwise reactions with isolation of inter- consistent with those calculated form the known crystal struc-
mediates, one-pot reactions with sequential addition of ture of the expected product Re(CO)5Cl (3a, Fig. 1b).‡28
reagents (also known as “telescoping” reactions),22 and one-pot
Similar behavior was also observed for reactions involving
multi-component reactions in which oxidative addition and NaBr and NaI as halide sources. To isolate the organometallic
ligand exchange are taking place with all reagents present. In products 3a–c, the reaction mixture was treated with acetone,
addition, by using rhenium(I) carbonyl halides as model targets leaving behind the inorganic residue formed by reduction of
for mechanochemical oxidative addition, we show how mech- Oxone. The residue was separated by simple ltration to provide
anochemistry can be coupled with sublimation to provide a 3a–c in excellent isolated yields (86–95%; Table 1, entries 1–3). As
high-yielding and completely solvent-free procedure for organ- a proof-of-principle, the synthesis of the bromide 3b was also
ometallic synthesis and product isolation.
performed on a 10-times larger scale, using one gram of 1. Again,
As the rst entry into mechanochemical oxidation of zer- the product 3b was obtained in excellent 91% isolated yield aer
ovalent metal carbonyls, we explored the synthesis of penta- only 15 min milling followed by washing (Table 1, Entry 4).‡
carbonylrhenium(I)- and pentacarbonylmanganese(I)- halides,
Mechanochemical reactivity was readily expanded to analo-
M(CO)5X (M ¼ Re, Mn; X ¼ Cl, Br, I) from Re2(CO)10 (1) and gous pentacarbonylmanganese(I) halides 4a–c, which were all
Mn2(CO)10 (2), respectively. While simple, these halides are also readily synthesized mechanochemically starting from 2. The
very suitable targets for a proof-of-principle study because of the products aer work-up were additionally characterised by PXRD
existing veried and standardised solution-based synthetic and Fourier-transform infrared attenuated total reectance
procedures.23 Most importantly, these halides are ubiquitous as (FTIR-ATR) spectra, which were consistent with those reported
precursors of luminescent rhenium organometallics,24 cata- in the literature. The previously not reported crystal structures
lysts25 and complexes of [Re(CO)3]+ which are valuable models of 3c and 4b were obtained by X-ray diffraction on single crystals
for comprehensive characterisation and in vitro assessment of grown from solution.§
99mTc complexes used for radiopharmaceutical and imaging
applications.26
In all cases the PXRD pattern of the reaction mixture
immediately aer milling clearly exhibited reections consis-
tent with those simulated for the crystal structures of 3a–c and
4a–c demonstrating that product formation takes place via
mechanochemical solvent-free oxidation rather than through
subsequent washing (Fig. 1, also ESI Fig. S20–S25†).
Results and discussion
Mechanochemical oxidative addition of metal carbonyls:
With the exception of Mn(CO)5I (4c), all mechanochemical
reactions provided the expected products rapidly (5 min
milling) and in isolated yields greater than or comparable to
those reported in the veried solution-based syntheses.23
Importantly, the quick mechanochemical procedures
completely eliminated the need for elementary halogens (3b, 3c,
4a, 4b), halogenated solvents or photolytic activation (3a, 3c)
that are central to the standard synthetic procedures.23 The
synthesis of 4c was the only case in which mechanosynthesis
gave a poorer yield than the solution synthesis. Reaction effi-
ciency was not improved by exploring alternative iodide sources
such as CuI, N-iodosuccinimide, tetraethylammonium (TEA)
solvent-free synthesis and separation
Milling of 1, Oxone®11,27 and sodium chloride (respective molar
ratios 1 : 1.5 : 2) in a tungsten carbide milling jar using a single
ball of 10 mm diameter. The powder X-ray diffraction (PXRD)
pattern of the reaction mixture aer 5 min milling revealed the
complete disappearance of X-ray reections corresponding to 1
and the concomitant appearance of new diffraction features
Table 1 Mechanochemical halogenation reaction of 1 and 2 using
Oxonea
Entry NaX
Metal Product Yield (%) Yield lit.d (%)
1
2
3
4
5
6
7
NaCl
NaBr Re
NaI Re
NaBre Re
NaCl Mn
NaBr Mn
NaIf
Mn
Re
3a
3b
3c
3b
4a
4b
4c
95b (86)c
94b (81)c
86b (71)c
91b
85%, hn, CCl4
91%, Br2, CS2
80%, hn, I2, hexane
78b
65%, Cl2, CCl4
90%, Br2, CS2
(A) 50%, I2, (B) 75–82%,
1st step Na(Hg),
88b
28b
THF; 2nd step I2, THF
Fig. 1 (a) General mechanochemical halogenation of 1 and 2. (b)
PXRD patterns (from top to bottom): measured for reactant Re2(CO)10
(1); simulated for the published Re(CO)5Cl structure (CCDC FOH-
CAG)28 and measured for the reaction mixture of 1, Oxone® and NaCl
after 5 min milling.
a
Reaction conditions: M2(CO)10 (100 mg), NaX (2 equiv.), Oxone (1.5
b
equiv.), 5 min of milling at 30 Hz frequency. Isolated yield aer
c
d
e
ltration. Isolated yield aer sublimation. See ref. 23. Reaction
performed using 1.0 g of Re2(CO)10 15 min milling. f 30 min milling.
Chem. Sci.
This journal is © The Royal Society of Chemistry 2014

View Article Online
Edge Article
Chemical Science
iodide or elemental iodine. However, the synthesis of 4c is
challenging even in solution, and achievement of high yields
requires a multi-step procedure involving sodium amalgam.23b
Whereas the demonstrated mechanosynthesis are entirely
solvent-free, the formation of ionic byproducts of Oxone®
reduction (K2SO4 and KHSO4) requires solvent-based product
separation. The use of solvent for product purication oen
diminishes their value as solvent-free processes. Recently,
however, we proposed that in some cases the vapour pressure of
the product might be sufficiently high enough to achieve
solvent-free isolation by sublimation.29 Indeed, all three penta-
carbonylrhenium(I) halides 3a–c could be isolated from the
mechanochemical reaction mixture by sublimation in very good
yields (71–86%, Table 1, entries 1–3).
Multi-step 3- and 4-component mechanosynthesis
The efficient mechanochemical syntheses of 3a–c and 4a–c are
expected to enable the design of multi-step mechanochemical
routes to diverse complexes starting from metal carbonyls. As
our rst entry into such transformations, we evaluated the
ability to mechanochemically exchange the carbonyl ligands
with neutral or anionic species, leading to target compounds
with fac-geometry of carbonyl ligands. As the simplest example
of such reactivity, we focused on the synthesis of fac-
[Re(CO)3Br3][TEA]2 (5, Scheme 1) normally obtained in solu-
tion30 by heating Re(CO)5Br (3b) with an excess of tetraethy-
Fig. 2 PXRD patterns for the synthesis of fac-[Re(CO)3Br3][TEA]2 5: (a)
simulated for the published structure of reactant 3b (CCDC FOW-
TOA);31a (b) simulated for the reported crystal structure of 5 (CCDC
YUJSAX10)31b and (c) measured for the reaction of 3b and TEAB after
3 hours milling. (d) Simulated PXRD pattern for the published structure
of 3a (CCDC FOHCAG);28 (e) simulated PXRD pattern for the published
structure of fac-PhenRe(CO)3Cl (6) (CCDC UGUSAQ01)32 and (f) PXRD
pattern measured for the reaction mixture of 3a and Phen after 3 h of
milling.
lammonium
bromide
(TEAB).
We
rst
explored
mechanosynthesis of 5 through a stepwise strategy, involving
the above established mechanosynthesis and isolation of 3b,
followed by mechanochemical reaction of 3b with 2.5 equiva-
lents of TEAB. Aer 3 h milling, the latter step afforded the
expected complex 5 in 82% yield (Fig. 2a–c).
As an alternative, we attempted the synthesis in a one-pot
sequential manner, by conducting the mechanochemical
synthesis of 3b for 5 minutes, immediately followed by the
addition of stoichiometric TEAB and milling for further 3 hours.
This simplied procedure, which does not require the isolation
of the intermediate, provided 5 in a 78% yield. Finally, the
similarity of ligands in 3b and 5 allowed the synthesis to be
performed using the simplest one-pot multi-component
procedure in which 1, Oxone and TEAB (molar ratio 1 : 1.5 : 7)
were milled for 3 hours. This one-pot multicomponent reaction
strategy gave 5 in 84% isolated yield directly from 1.
Following the successful synthesis of fac-[Re(CO)3Br3][TEA]2
we addressed the synthesis of a fac-tricarbonyl complex with two
different additional ligands. A search of the Cambridge Struc-
tural Database (CSD)32 led us to select the mixed complex
involving carbonyl, chloride and 1,10-phenanthroline (Phen)
ligands as the most suitable candidate. Mechanosynthesis of
fac-PhenRe(CO)3Cl
6 was rst attempted by milling the
mechanochemically obtained 3a and Phen (Scheme 2).
Aer 3 h of milling, PXRD analysis of the solid reaction
mixture (Fig. 2d–f) clearly revealed the presence of the expected
product 6,33 isolated in 68% yield aer purication. Thus, the
overall yield for this two-step synthesis was 65%.
A one-pot sequential synthesis from Re2(CO)10 (1) without
intermediate isolation of 3a was conducted by rst milling 1,
Oxone and NaCl for 5 min, followed by the addition of one
equivalent Phen per rhenium atom and milling for 3 h. Such a
procedure provided 5 in a comparable 61% yield. Importantly,
the reaction also produced small amounts of a previously not
observed byproduct 7. The simplest synthetic procedure
involved one-pot multi-component solvent-free milling together
of 1, Oxone, NaCl and Phen for three hours. This one-pot
Scheme 1 Comparison of mechanochemical syntheses of the rhe-
nium(I) complex 5 through one-pot, two-steps or one-pot sequential
approaches.
This journal is © The Royal Society of Chemistry 2014
Chem. Sci.

View Article Online
Chemical Science
Edge Article
compounds of manganese. Indeed, the mechanochemical
reaction of Mn(CO)5Cl (4a, obtained from Mn2(CO)10 mecha-
nochemically) and 2,20-bipyridine readily provided the expected
fac-(2,20-bipyridine)Mn(CO)3Cl (8) in 68% yield (see ESI†).
Mechanosynthesis of uoride complexes: one-pot reactions
with up to ve components
Next, we focused on the synthesis of rhenium carbonyl
complexes containing uoride ligands. Synthetic approaches
for such compounds are more challenging than for other
halides, because of the general sensitivity of Re(CO)5F (3d),
which has never been isolated in the solid state, as well as
because Oxone cannot be employed for the oxidation of alkali
uorides. The simple compound 3d was originally prepared by
non-oxidative exchange of halides between Re(CO)5Cl and HF.34
Compound 3d is highly labile and was never isolated, but used
as a transient precursor for the synthesis of different uoro-
complexes such as (2,20-azobispyridine)Re(CO)3F.35
With the intention to demonstrate the mechanochemical
synthesis of all members of the pentacarbonylrhenium halide
family, we explored the mechanochemical exchange of halide
ligands between Re(CO)5I 3c and AgF (Fig. 4a). Aer 30 min of
milling, the reaction provided a dark brown powder. The PXRD
analysis of the product revealed the absence of the reactant 3c
and appearance of AgI, indicating that the expected ligand
exchange indeed took place (Fig. 4a–c). No other features were
noticeable in the pattern, indicating that the organometallic
product was amorphous. Consistent with the reported insta-
bility of 3d, attempts to separate AgI from the mechanochem-
ical product by washing led to decomposition: washing of the
reaction mixture with either acetone or dichloromethane
generated a red-brown solution with frothing and a precipitate
that was identied aer ltration as AgI using PXRD. Rotary
evaporation of the ltrate gave a solid that was identied by
HRMS and 1H NMR as the tetranuclear m3-hydroxo cubane
cluster [Re(CO)3]4(OH)4 (9).36 Specically, HRMS revealed a
molecular ion in the negative mode with a m/z ratio of
1148.7463, consistent with the singly deprotonated anion of
[Re(CO)3]4(OH)4. The 13C NMR spectrum matched to the one
reported for 9 in the literature, which was also consistent with
the spectrum of a separately prepared sample of 9.36 The 19F
NMR spectrum was silent indicating the absence of uorine in
the product.
Scheme 2 Comparison of mechanochemical syntheses of the rhe-
nium(I) complex 6 through one-pot, two-steps or one-pot sequential
approaches.
four-component procedure successfully provided the desired
product 6 in a slightly reduced yield of 56%, again with a small
quantity of the byproduct 7. We note that a one-pot four-
component mechanochemical synthesis involving the rear-
rangement of covalent bonds and, indeed, oxidation states of
reactants has never previously been explored.
Recrystallisation of the byproduct
7 from acetonitrile
provided single crystals of an acetonitrile solvate of 7 suitable
for X-ray single crystal diffraction analysis. The resulting crystal
structure revealed that 7 exhibits the identical ratio of Phen and
Re as 6, but is composed of cis-[(Phen)2Re(CO)2]+ cations and
ReO4ꢀ anions (Fig. 3).§ It remains unclear why compound 7 was
formed in 4% and 7% yields when using the one-pot sequential
and one-pot multi-component synthetic strategy. As 7 does not
contain any chloride ions, we attempted to conduct its targeted
mechanosynthesis by milling together 1, Oxone and Phen.
However, no reaction was observed in these experiments and
the reactant 1 was readily recovered.
Whereas our synthetic interests are in the chemistry of
rhenium, we also explored whether the mechanochemical
ligand exchange reaction could also be performed with
The formation of [Re(CO)3]4(OH)4 and frothing upon disso-
lution of the mechanochemical product can be explained by
hydrolysis coupled with decarbonylation and loss of HF from
labile 3d in the presence of moisture. Indeed, if the mechano-
chemical product aer washing was ground in air, X-ray
reections consistent with the published structure of 9$4H2O
appeared in the PXRD pattern (Fig. 4d and e).37
However, if the freshly milled reaction mixture was opened
in a glove box to exclude moisture and directly extracted into
acetone-d6, the 19F NMR spectrum of the sample revealed a
single resonance, at ꢀ272.5 ppm (with respect to CFCl3)
(Fig. 4h), consistent with the expected product 3d. To further
support the formation of 3d, we conducted immediate MS
Fig. 3 An ORTEP view (thermal ellipsoids shown at 30% probability
level) of the asymmetric unit of the acetonitrile solvate of cis-
[(Phen)2Re(CO)2][ReO4] (7).§
Chem. Sci.
This journal is © The Royal Society of Chemistry 2014

View Article Online
Edge Article
Chemical Science
Scheme
3
Comparison of mechanochemical syntheses of 10,
demonstrating a direct five-component, one-pot and solvent-free
route to 10 from the carbonyl 1.
more stable complex, related to 3d. In particular, the fac-tri-
carbonylrhenium(I) uoride complex with N,N,N0,N0-tetra-
methylethylenediamine (TMEDA), fac-(TMEDA)Re(CO)3F 10 was
selected on the basis of structural similarity to 3d and avail-
ability of crystal structure in the CSD.38 Synthesis was initially
attempted in a one-pot sequential fashion from the mecha-
nochemically prepared Re(CO)5I, rst by addition of AgF and
milling, followed by the addition of TMEDA and milling further
for 90 min. Aer milling, the analysis of the reaction mixture by
PXRD revealed the formation of the uorinated complex (Fig. 4f
and g), and the expected product 10 was isolated in 70% yield
(overall 60% from mechanochemically obtained 1) (Scheme 3).
The reaction could also be conducted in one-pot multi-
component fashion from 3c (Scheme 1), by milling a mixture of
3c, AgF and TMEDA for 2 h. This resulted in the isolation of
compound 10 in a higher, 79% yield (68% overall yield from 1).
The 19F NMR of the pure complex 10 showed the presence of
just one peak at ꢀ256 ppm (Fig. 4i). The complex 10 was also
1
fully characterized by H, 13C NMR, PXRD, FTIR-TAR and MS
analysis. It was particularly pleasing, however, to see that
compound 10 could be prepared in a good yield (45%) by a
simple one-pot multi-component reaction directly from the
rhenium carbonyl, by milling 1 with Oxone, sodium iodide,
silver uoride and TMEDA.
To the best of our knowledge, the synthesis of 10 is the only
example of a molecule synthesized by a ve-component mech-
Fig. 4 (a) Non-oxidative halogen exchange reaction of 3c and synthesis
of fac-(TMEDA)Re(CO)3F (10). PXRD patterns: (b) simulated for the
reactant Re(CO)3I (3c) based on herein reported structure; (c) measured anochemical reaction involving transformations of covalent
bonds and redox chemistry.39
for the reaction mixture of 3c and AgF after 30 min of milling; (d)
measured for the product under (c), after washing with acetone and
grinding in air; (e) simulated for the published structure of 9$4H2O
(CCDC RADWID);37 (f) measured for the reaction mixture of Re(CO)3I
Conclusions
(3c), AgF and TMEDA after 2 hours milling; (g) simulated for the published
structure of fac-(TMEDA)Re(CO)3F (10) (CCDC COLWAB).38 (h) 19F-NMR
The work presented here demonstrates the design of multi-step
spectrum of Re(CO)5F (3d) dissolved in acetone-d6 in the absence of air;
and multi-component mechanochemical reaction sequences by
(i) 19F-NMR spectrum of (TMEDA)Re(CO)3F (10) in acetone-d6.
combining redox and ligand exchange reactions. The imme-
diate benet of the herein explored modes of multi-component
mechanochemical reactivity is to advance solvent-free and
analysis of the freshly washed mixture which revealed weak environmentally-friendly organometallic synthesis, by permit-
signals for [Re(CO)3(OH)]4 but, in positive mode, signals cor- ting rapid and solvent-free construction of complex targets
responding to 3d + Na+ (m/z ¼ 368.9169) and (3d-CO)+Na+ directly from the simplest reactants, e.g., metal carbonyls. Most
(m/z ¼ 340.9218) were clearly visible (see ESI†). Thus, the 19F targets in this proof-of-principle study are interesting in the
NMR and MS data support the formation of a highly moisture- context of developing model radiopharmaceuticals containing
sensitive Re(CO)5F 3d species by mechanochemistry.
the fac-Re(CO)3 species. However, the synthesis of (N,N,N0,N0-
To fully ascertain the ability to synthesise uorinated tetramethylethylenediamine)(tricarbonyl)rhenium(I) uoride is
complexes by mechanochemistry, we explored the synthesis of a particularly signicant as an example of mechanochemical
This journal is © The Royal Society of Chemistry 2014
Chem. Sci.

View Article Online
Chemical Science
Edge Article
synthesis of a complex organometallic species directly from a
metal carbonyl. In particular, it is a so far unique example of a
molecule produced by a ve-component transformation in one
milling step. In the broader context, this study represents a
signicant advance in complexity of mechanochemical reaction
designs and we believe will encourage further exploration of
multi-component, multi-step mechanochemical reaction
sequences required for the development of solvent-free chem-
istry as a true alternative to established solvent-based processes.
F. Grepioni, L. Maini, P. P. Mazzeo and B. Ventura, New J.
Chem., 2011, 35, 339.
4 (a) D. Braga, L. Maini and F. Grepioni, Chem. Soc. Rev., 2013,
42, 7638; (b) D. R. Weyna, T. Shattock, P. Vishweshwar and
M. J. Zaworotko, Cryst. Growth Des., 2009, 9, 1106; (c)
D. J. Berry, C. C. Seaton, W. Clegg, R. W. Harrington,
S. J. Coles, P. N. Horton, M. B. Hursthouse, R. Storey,
ˇˇ ´
W. Jones, T. Friscic and N. Blagden, Cryst. Growth Des.,
ˇˇ ´
´ ´
2008, 8, 1697; (d) T. Friscic, R. W. Lancaster, L. Fabian and
P. G. Karamertzanis, Proc. Natl. Acad. Sci. U. S. A., 2010,
107, 13216; (e) D. Braga, F. Grepioni and G. I. Lampronti,
CrystEngComm, 2011, 13, 3122.
Acknowledgements
We acknowledge nancial support of NSERC Discovery Grants,
Canada Foundation for Innovation Leader's Opportunity Fund
(CFI-LOF), the FRQNT Centre for Self-assembled Chemical
Structures (CSACS) and the FRQNT Nouveaux Chercheurs
program. Prof. D. S. Bohle, Cristina Mottillo and Dr A. D. Kat-
senis are acknowledged for aid in obtaining single crystal data,
Dr F. Morin for help in obtaining NMR spectra, and Dr A.
Wahba for collecting MS data.
´
5 (a) B. Rodrıguez, A. Bruckmann, T. Rantanen and C. Bolm,
Adv. Synth. Catal., 2007, 349, 2213; (b) K. Tanaka and
F. Toda, Chem. Rev., 2000, 100, 1025.
6 F. Schneider, T. Szuppa, A. Stolle, B. Ondruschka and
H. Hopf, Green Chem., 2009, 11, 1894.
7 (a) V. Strukil, D. Margetic, M. D. Igrc, M. Eckert-Maksic and
ˇ
´
´
ˇˇ ´
T. Friscic, Chem. Commun., 2012, 48, 9705; (b)
G. A. Bowmaker, N. Chaichit, C. Pakawatchai,
B. W. Skelton and A. H. White, Dalton Trans., 2008, 2926;
ˇ
´
ˇˇ ´
(c) V. Strukil, M. D. Igrc, M. Eckert-Maksic and T. Friscic,
Notes and references
¨
Chem. – Eur. J., 2012, 18, 8464; (d) C. B. Aakeroy and
‡ Varying the amount of Oxone® can have a strong effect on the reaction yield.
Initial attempts to optimise the synthesis of M(CO)5X (M-Re, Mn; X ¼ Cl, Br, I)
revealed that using >2 equivalents of Oxone® decreased the yields of reactions. In
order to better understand this effect we performed additional reactions involving
only the metal carbonyl or only the pre-made M(CO)5X (M-Re, Mn; X ¼ Cl, Br, I)
and Oxone® as the reactants. In all cases the carbonyl reactants could no longer be
completely recovered, indicating they can undergo side-reactions with excess
Oxone®. For that reason, the amount of Oxone® was xed in subsequent opti-
mization reactions and was not explored as a reaction parameter in further
exploration of multi-step and one-pot reactions.
ˇ
P. D. Chopade, Org. Lett., 2011, 13, 1; (e) V. Strukil,
´
´
L. Fabian, D. G. Reid, M. J. Duer, G. J. Jackson, M. Eckert-
Maksic and T. Friscic, Chem. Commun., 2010, 46, 9191.
8 For recent organometallic transformations
mechanochemistry, see: (a) J. D. Egbert, A. M. Z. Slawin
and S. P. Nolan, Organometallics, 2013, 32, 2271; (b)
J. Lewinski, M. Dutkiewicz, M. Lesiuk, W. Slivinski,
K. Zelga, I. Justyniak and J. Lipkowski, Angew. Chem., Int.
Ed., 2010, 49, 8266; (c) D. Cincic, M. Juribasic, D. Babic,
K. Molcanov, P. Sket, J. Plavec and M. Curic, Chem.
Commun., 2011, 47, 11543; (d) C. S. B. Gomes, P. T. Gomes
and M. T. Duarte, J. Organomet. Chem., 2014, 760, 101; (e)
M. C. Blanco, J. Camara, M. C. Gimeno, A. Laguna,
S. L. James, M. C. Lagunas and M. D. Villacampa, Angew.
Chem., Int. Ed., 2012, 51, 9777.
´
ˇˇ ´
by
´
´
´
ˇ ´
ˇ ´
´
˚
§ Crystal data: 3c, C5O5IRe, CCDC 997709, orthorhombic, a ¼ 7.6549(7) A, b ¼
3
ˇ
´
˚
˚
˚
ˇ
´
11.103(1) A, c ¼ 10.989(1) A, V ¼ 934.0(2) A , space group Cmcm, Z ¼ 4, R1 ¼ 0.0165,
wR2 ¼ 0.0389 (for I > 2sI), S ¼ 1.190; 4b, C5O5BrMn, CCDC 997710, orthorhombic,
3
˚
˚
˚
˚
a ¼ 11.772(2) A, b ¼ 11.507(2) A, c ¼ 6.1089(8) A, V ¼ 827.5(2) A , space group
Pnma, Z ¼ 4, R1 ¼ 0.0278, wR2 ¼ 0.0749 (for I > 2sI), S ¼ 1.051; 7, C28H19N5O6Re2,
´
˚
˚
˚
CCDC 997711, monoclinic, a ¼ 12.6739(6) A, b ¼ 11.2202(6) A, c ¼ 19.9289(1) A,
3
ꢁ
˚
b ¼ 104.719(1) , V ¼ 2741.0(2) A , space group P21/n, Z ¼ 4, R1 ¼ 0.0323, wR2
0.0499 (for I > 2sI), S ¼ 1.017.
¼
9 (a) D. Braga, S. L. Giaffreda and F. Grepioni, Chem. Commun.,
2006, 3877; (b) D. Braga, S. L. Giaffreda, F. Grepioni,
A. Pettersen, L. Maini, M. Curzi and M. Polito, Dalton
Trans., 2006, 1249.
1 (a) S. L. James, C. J. Adams, C. Bolm, D. Braga, P. Collier,
ˇˇ ´
T. Friscic, F. Grepioni, K. D. M. Harris, G. Hyett, W. Jones,
A. Krebs, J. Mack, L. Maini, A. G. Orpen, I. P. Parkin,
W. Ch. Shearouse, J. W. Steed and D. C. Waddell, Chem. 10 (a) M. D. Bala and N. J. Coville, J. Organomet. Chem., 2007,
Soc. Rev., 2012, 41, 413; (b) E. Boldyreva, Chem. Soc. Rev.,
692, 709; (b) M. D. Bala, A. Budhai and N. J. Coville,
Organometallics, 2004, 23, 2048; (c) N. J. Coville and
L. Cheng, J. Organomet. Chem., 1998, 571, 149.
ˇˇ ´
2013, 42, 7719; (c) T. Friscic, Chem. Soc. Rev., 2012, 41, 3493.
2 (a) A. Stolle, T. Szuppa, S. E. S. Leonhardt and
´
B. Ondruschka, Chem. Soc. Rev., 2011, 40, 2317; (b) 11 J. G. Hernandez, N. A. J. Macdonald, C. Mottillo, I. S. Butler
ˇˇ ´
R. B. N. Baig and R. S. Varma, Chem. Soc. Rev., 2012, 41, 1559.
ˇˇ ´
and T. Friscic, Green Chem., 2014, 16, 1087.
´
3 (a) T. Friscic, D. G. Reid, I. Halasz, R. S. Stein, R. E. Dinnebier 12 (a) T.-X. Metro, J. Bonnamour, T. Reidon, J. Sarpoulet,
and M. J. Duer, Angew. Chem., Int. Ed., 2010, 49, 712; (b)
B. P. Biswal, S. Chandra, S. Kandambeth, B. Lukose,
T. Heine and R. Banerjee, J. Am. Chem. Soc., 2013, 135,
J. Martinez and F. Lamaty, Chem. Commun., 2012, 48,
ˇ
´
11781; (b) V. Strukil, B. Bartolec, T. Portada, I. Đilovic,
I. Halasz and D. Margetic, Chem. Commun., 2012, 48, 12100.
ˇ
ˇˇ ´
ˇˇ ´
5328; (c) T. Friscic, J. Mater. Chem., 2010, 20, 7599; (d) 13 D. Tan, V. Strukil, C. Mottillo and T. Friscic, Chem. Commun.,
A. Lazuen Garay, A. Pichon and S. L. James, Chem. Soc.
Rev., 2007, 36, 846; (e) D. Braga and F. Grepioni, Chem. 14 (a) D. Cincic, I. Brekalo and B. Kaitner, Chem. Commun.,
2014, 50, 5248.
ˇ ´
Commun., 2005, 3635; (f) L. Maini, D. Braga, P. P. Mazzeo
and B. Ventura, Dalton Trans., 2012, 41, 531; (g) D. Braga,
2012, 48, 11683; (b) G. Rothenberg, A. P. Downie,
C. L. Raston and J. L. Scott, J. Am. Chem. Soc., 2001, 123, 8701.
Chem. Sci.
This journal is © The Royal Society of Chemistry 2014

View Article Online
Edge Article
Chemical Science
15 D. A. Fulmer, W. C. Shearouse, S. T. Mendoza and J. Mack,
Green Chem., 2009, 11, 1821.
E. Malveaux, X. Xu, L. G. Marzilli and A. Taylor, J. Nucl.
Med., 2006, 47, 1032; (c) S. James, K. P. Maresca,
J. W. Babich, J. F. Valliant, L. Doering and J. Zubieta,
Bioconjugate Chem., 2006, 17, 590; (d) K. A. Stephenson,
S. R. Banerjee, T. Besanger, O. O. Sogbein, M. K. Levadala,
N. McFarlane, J. A. Lemon, D. R. Boreham, K. P. Maresca,
J. D. Brennan, J. W. Babich, J. Zubieta and J. F. Valliant,
J. Am. Chem. Soc., 2004, 126, 8598; (e) R. Schibli and
P. A. Schubiger, Eur. J. Nucl. Med., 2002, 29, 1529.
16 (a) F. Schneider and B. Ondruschka, ChemSusChem, 2008, 1,
622; (b) F. Schneider, A. Stolle, B. Ondruschka and H. Hopf,
Org. Process Res. Dev., 2009, 13, 44; (c) F. Bernhardt,
R. Trotzki, T. Szuppa, A. Stolle and B. Ondruschka,
Beilstein J. Org. Chem., 2010, 6, 7; (d) S. F. Nielsen,
D. Peters and O. Axelsson, Synth. Commun., 2000, 30, 3501.
17 R. Thorwirth, A. Stolle, B. Ondruschka, A. Wild and
U. S. Schubert, Chem. Commun., 2011, 47, 4370.
27 For the halogenation of organic residues using Oxone®, see:
(a) R. Schmidt, A. Stolle and B. Ondruschka, Green Chem.,
2012, 14, 1673; (b) G.-W. Wang and J. Gao, Green Chem.,
2012, 14, 1125.
18 J. Bonnamour, T.-X. Metro, J. Martinez and F. Lamaty, Green
Chem., 2013, 15, 1116.
¨
¨
19 (a) B. Içli, N. Christinat, J. Tonnemann, C. Schuttler,
R. Scopelliti and K. Severin, J. Am. Chem. Soc., 2009, 131, 28 W. A. Cotton and L. M. Daniels, Acta Crystallogr., Sect. C:
3154; (b) M. Pascu, A. Ruggi, R. Scopelliti and K. Severin,
Chem. Commun., 2013, 49, 45.
20 (a) M. Ferguson, N. Giri, X. Huang, D. Apperley and
Cryst. Struct. Commun., 1983, 39, 1495.
´
ˇˇ ´
ˇ
29 (a) I. Huskic, I. Halasz, T. Friscic and H. Vancik, Green Chem.,
2012, 14, 1597; (b) H. Shy, P. Mackin, A. S. Orvieto,
D. Gharbharan, G. R. Peterson, N. Bampos and
T. D. Hamilton, Faraday Discuss., 2014, DOI: 10.1039/
c3fd00140g.
ˇˇ ´
S. L. James, Green Chem., 2014, 16, 1374; (b) T. Friscic,
ˇ
ˇ
ˇ
´
´ ´
E. Mestrovic, D. Skalec Samec, B. Kaitner and L. Fabian,
Chem. – Eur. J., 2009, 15, 12644; (c) G.-W. Wang and J. Gao,
Org. Lett., 2009, 11, 2385; (d) W. C. Shearouse, C. M. Korte 30 R. Alberto, A. Egli, U. Abram, K. Hegetschweiler, V. Gramlich
and J. Mack, Green Chem., 2011, 13, 598; (e) N. Giri, and P. A. Schubiger, J. Chem. Soc., Dalton Trans., 1994, 2815.
C. Bowen, J. S. Vyle and S. L. James, Green Chem., 2008, 10, 31 (a) M. C. Couldwell and J. Simpson, Cryst. Struct. Commun.,
627; (f) Z. Zhang, G.-W. Wang, C.-B. Miao, Y.-W. Dong and
Y.-B. Shen, Chem. Commun., 2004, 1832; (g) E. Y. Cheung,
S. J. Kitchin, K. D. M. Harris, Y. Imai, N. Tajima and
R. Kuroda, J. Am. Chem. Soc., 2003, 125, 14658.
1977, 6, 1; (b) R. Alberto, R. Schibli, A. Egli,
P. A. Schubiger, W. A. Herrmann, G. Artus, U. Abram and
T. A. Kaden, J. Organomet. Chem., 1995, 493, 119.
´
32 A. A. Martı, G. Mezei, L. Maldonado, G. Paralitici,
´
R. G. Raptis and J. L. Colon, Eur. J. Inorg. Chem., 2005, 118.
21 For a recent overview of the concept of orthogonality in
´
chemical
synthesis,
see:
C.
H.
Wong
and 33 M. K. Itokazu, A. S. Polo, D. L. Araujo de Faria, C. A. Bignozzi
S. C. Zimmerman, Chem. Commun., 2013, 49, 1679.
and N. Y. Murakami Iha, Inorg. Chim. Acta, 2001, 313, 149.
22 (a) D. Belmessieri, D. B. Cordes, A. M. Z. Slawin and 34 (a) T. A. O'Donnell, K. A. Phillips and A. B. Waugh, Inorg.
A. D. Smith, Org. Lett., 2013, 15, 3472; (b) A. A. Desai,
E. J. Molitor and J. E. Anderson, Org. Process Res. Dev.,
2011, 16, 160; (c) R. C. Cioc, E. Ruijter and R. V. A. Orru,
Green Chem., 2014, 16, 2958.
Chem., 1973, 12, 1435; (b) D. M. Bruce, A. J. Hewitt,
J. H. Holloway, R. D. Peacock and I. L. Wilson, J. Chem.
Soc., Dalton Trans., 1976, 2230; (c) For an alternative
methodology see: K. Raab and W. Beck, Chem. Ber., 1985,
118, 3830.
23 (a) S. P. Schmidt, W. C. Trogler and F. Basolo, Inorg. Synth.,
1990, 28, 164; (b) K. J. Reimer and A. Shaver, Inorg. Synth., 35 S. Frantz, J. Fiedler, I. Hartenbach, T. Schleid and W. Kaim,
1990, 28, 154. J. Organomet. Chem., 2004, 689, 3031.
24 (a) K. K.-W. Lo, K. Y. Zhang and S. P.-Y. Li, Eur. J. Inorg. 36 (a) M. Herberhold and G. Suss, Angew. Chem., Int. Ed. Engl.,
¨
¨
1975, 14(4), 700; (b) M. Herberhold, G. Suss, J. Ellermann
Chem., 2011, 3551; (b) E. Baggaley, J. A. Weinstein and
J. A. Gareth Williams, Coord. Chem. Rev., 2012, 256, 1762;
¨
and H. Gabelein, Chem. Ber., 1978, 111, 2931.
(c) Y. Matsubara, S. E. Hightower, J. Chen, D. C. Grills, 37 N. Lazarova, S. James, J. Babich and J. Zubieta, Inorg. Chem.
D. E. Polyansky, J. T. Muckerman, K. Tanaka and E. Fujita, Commun., 2004, 7, 1023.
Chem. Commun., 2014, 50, 728; (d) B. A. Frenzel, 38 E. Horn and M. R. Snow, Aust. J. Chem., 1984, 37, 35.
J. E. Schumaker, D. R. Black and S. E. Hightower, Dalton 39 A ve-component milling reaction involving neutralization
Trans., 2013, 42, 12440.
and supramolecular self-assembly was utilized to
synthesize a crystalline solvate of a magnesium complex,
25 Y. Kuninobu and K. Takai, Chem. Rev., 2011, 111, 1938.
26 (a) D. J. Hayne, S. Lim and P. S. Donelly, Chem. Soc. Rev.,
2014, DOI: 10.1039/c4cs00026a; (b) M. Lipowska, H. He,
ˇˇ ´
see: E. H. H. Chow, F. C. Strobridge and T. Friscic, Chem.
Commun., 2010, 46, 6368.
This journal is © The Royal Society of Chemistry 2014
Chem. Sci.