ChemComm
View Article Online
COMMUNICATION
[(NHC)CoR2]: pre-catalysts for homogeneous
Published on 26 November 2018. Downloaded by University of Edinburgh on 1/21/2019 11:53:25 AM.
olefin and alkyne hydrogenation†
Cite this: Chem. Commun., 2018,
54, 13798
Andreea Enachi, Dirk Baabe, Marc-Kevin Zaretzke, Peter Schweyen,
Received 7th November 2018, Matthias Freytag, Jan Raeder and Marc D. Walter *
Accepted 19th November 2018
DOI: 10.1039/c8cc08891h
rsc.li/chemcomm
A novel synthesis for dialkyl cobalt compounds [(tmeda)CoR2] is
presented. In these complexes tmeda is readily replaced by an NHC
or a bidentate phosphine ligand to form 3- and 4-coordinate
compounds, respectively. [(ItBu)Co(CH2SiMe3)2] (ItBu = 1,3-di-tert-
butylimidazolin-2-ylidene) serves as an efficient, homogeneous
olefin hydrogenation pre-catalyst and allows the preparation of
the novel cobalt bis(alkyne) complex [(ItBu)Co(g2-PhCCPh)2].
The replacement of precious metals in catalysis by earth-
abundant 3d-transition metals such as Fe, Co and Ni represents
a flourishing and highly topical field of chemical research.1–10
As part of this endeavour, these metals have been successfully
utilised in hydrogenation, hydrofunctionalisation and cross-
coupling reactions. Recently, the Chirik group introduced efficient
olefin hydrogenation catalysts based on dialkyl cobalt complexes
stabilised by bidentate phosphines such as [(P-P)Co(CH2SiMe3)2]
(P-P = dppe, depe, dmpe, dppBz).3,9–11 Alternatively, low-valent
Co(–I) species such as [(Z4-anthracene)2Co], [(Z4-naphthalene)-
Co(Z4-cod)] (cod = 1,5-cyclooctadiene) and [(Z4-cod)2Co] may
also be used.12 N-heterocyclic carbenes (NHCs) represent
an attractive alternative to ubiquitous phosphine ligands in
catalysis and small molecule activation.13–17 For example, NHC-
stabilised cobalt complexes have been applied, e.g. in the
catalytic olefin hydrosilylation with tertiary silanes,8,18,19 N2
functionalization,20 or Kumada cross-coupling reactions.2
Furthermore, starting from (NHC)Co fragments, NHC–silyl–
NHC pincer ligands,21 cobalt(0) bis(olefin),22,23 and cobalt
imido complexes24–26 were successfully prepared. In this
contribution we detail a novel and high-purity synthesis of
[(tmeda)CoR2] (R = CH2SiMe3 (1a), CH2CMe3 (1b) and CH2CMe2Ph
(1c)), which serve as excellent starting materials for ligand substitu-
tion reactions when treated with NHC or bidentate phosphine
Technische Universität Braunschweig, Institut für Anorganische und Analytische
Chemie, Hagenring 30, 38106 Braunschweig, Germany. E-mail: mwalter@tu-bs.de
† Electronic supplementary information (ESI) available: Experimental, catalytic
and crystallographic details; EPR and UV/Vis spectroscopic data; magnetic
susceptibility studies. CCDC 1863894–1863904. For ESI and crystallographic data
in CIF or other electronic format see DOI: 10.1039/c8cc08891h
13798 | Chem. Commun., 2018, 54, 13798--13801
View Journal | View Issue
ligands and therefore offer attractive alternatives to [(py)2CoR2].27 In
addition, [(ItBu)Co(CH2SiMe3)2] (ItBu = 1,3-di-tert-butylimidazolin-
2-ylidene; 2a-H) acts as an efficient, homogeneous olefin hydro-
genation pre-catalyst.
Treatment of [(tmeda)Co(acac)2]28 with MgR2 (R = CH2CMe3,
CH2SiMe3, CH2CMe2Ph)29,30 forms the dialkyl complexes 1a–c
in high purity and good yields (Scheme 1 and see ESI†).
This synthetic route significantly surpasses the previously
reported procedures for [(tmeda)Co(CH2SiMe3)2] proceeding
via [(py)2Co(CH2SiMe3)2], which is thermally sensitive and its
yield strongly depends on the quality and purity of the CoCl2
starting material.27,31 Compounds 1a–c were characterised (see ESI†)
by NMR, EPR and UV/Vis spectroscopy, elemental analyses and
solid-state magnetic susceptibility studies. Consistent with previous
studies on four-coordinate, tetrahedral dialkyl Co(II) species, the
complexes 1a–c adopt a high-spin configuration (S = 3/2) with
effective magnetic moments (meff) that range between meff (300 K) =
4.74 and 5.72 mB (Fig. 1 and see ESI†).32–36 These values are
significantly higher than the S = 3/2 spin-only value of 3.87 mB
implying substantial orbital contributions to meff, which is commonly
observed for high-spin Co(II) complexes.37 At temperatures below
T = ca. 100 K, the declining magnetic moment with decreasing
temperature is attributed to zero-field splitting (ZFS) and was further
analysed by a simplified spin-Hamiltonian approach (with rhombic
ZFS parameter E/D = 0) utilising anisotropic g-values with
gx = gy o gz (see ESI†). This analysis reveals average g-values
between g = 2.328 and 2.701, and positive values for the axial
ZFS parameter (D) in the range of D = +9.6 to +16.8 cm1.
Complexes 1a–c were treated with NHCs (ItBu = 1,3-di-tert-
butylimidazolin-2-ylidene; ItBuMe2 = 1,3-di-tert-butyl-4,5-
dimethylimidazolin-2-ylidene) and bidentate phosphines
Scheme 1 Synthesis of [(tmeda)CoR2] complexes 1a–c derived from
[(tmeda)Co(acac)2] and [MgR2].
This journal is © The Royal Society of Chemistry 2018
 View Article Online

Communication ChemComm
Published on 26 November 2018. Downloaded by University of Edinburgh on 1/21/2019 11:53:25 AM.

Fig. 1 Effective magnetic moment (meff) vs. T plots for 1a, 2a-Me, 4 and 5
recorded at temperatures between T = 2.6 and 300 K with an applied
magnetic field of Hext = 1 kOe. Symbols: experimental data; line: fit based
on a simplified spin-Hamiltonian approach (see text).

Fig. 2 Displacement ellipsoid plots (50% probability) for complexes 2a-H, 3, 4

and 5. Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and
angles (1): complex 2a-H: Co–C1 2.0569(16), Co–C12 2.0438(19), Co–C16
2.0308(19), C1–Co–C12 111.73(8), C12–Co–C16 119.82(8), C1–Co–C16
126.79(7). Complex 3: Co–P1 2.2181(6), Co–P2 2.1938(6), Co–C1 1.970(2),
Co–C8 2.003(2), P1–Co–P2 86.08(2), P2–Co–C8 90.43(7), C1–Co–C8
82.82(9). Complex 4: Co–P 2.2152(4), Co–C1 2.0359(15), P–Co–P0 86.98(2),
P0 –Co–C10 92.57(5), C1–Co–C10 88.73(9), P–Co–C1 92.57(5). Complex 5:
Co–C1 1.9678(19), Co–C7 1.9470(14), Co–C8 1.9196(13), C7–C8 1.282(2).

Scheme 2 Ligand substitution reactions based on compounds 1a–c.

Table 1 Olefin hydrogenation using 2a-H as pre-catalyst

(dippe = 1,2-bis(di-iso-propylphosphino)ethane; depe = 1,2-
Cat. loading Conv. %
bis(diethylphosphino)ethane) (Scheme 2). In all cases, tmeda Entry Substrate (mol%) (time) (yield %) Product
replacement proceeded smoothly, and complexes 2–4 were a
100
isolated in good yield and high-purity (Fig. 2 and see ESI†). 1 5 (27 h) (73)a
For the neophyl derivative 1c, the 5-membered metallacycle 3
was formed because of CH bond activation of the neophyl 100a
2 0.5 (6 h) (93)a
moiety (see ESI†). Tmeda exchange by one NHC does not alter
the spin-state (S = 3/2) of the Co(II) atom in 2a-H/Me and 2b-H/Me, 100a
3 0.5 (18 h) (100)b
whereas a replacement with bidentate phosphines such as depe
and dippe results in spin-pairing to yield the square-planar,
98a
low-spin (S = 1/2) compounds 3 and 4, whose X-band EPR (98)b
4 0.5 (18 h)
spectra and effective magnetic moments of meff (300 K) = 2.63
and 2.68 mB, respectively, are unexceptional (Fig. 1 and see
100a
ESI†).3 For the high-spin Co(II) compounds (2a-H/Me and 5 3 (49 h) (84)b
2b-H/Me), again, typical EPR spectra and meff (300 K) values in
the range between 4.47 and 5.04 mB (Fig. 1 and see ESI†) 22a
6 5 (26 h) (6)b
were obtained.38–41 The analysis of the temperature-dependent
effective magnetic moment was performed analogous to that of 25a
7 5 (20 h) (17)a
1a–c, revealing average g-values in the range between g = 2.162
13a
and 2.467, and negative D-values between D = 37 and 40 cm1 (7)a
8 0.5 (6 h)
for 2a-H/Me and 2b-H/Me (Fig. 1, and see ESI†).38–41
Similar to the reactivity of the related species [(P-P)CoR2]
a
(P-P = dppe, depe, dmpe),3 the three-coordinate NHC-adducts Determined by GC. b Determined by 1H NMR spectroscopy. c Product
distribution determined by 1H and 13C{1H} NMR spectroscopy.
[(NHC)CoR2] were probed in hydrogenation reactions. Complex
2a-H was exposed to H2 in the presence of various olefins at
ambient temperature and moderate H2 pressure (ca. 4 bar) (Table 1 the four-coordinate complexes [(P-P)Co(CH2SiMe3)2], were explicitly
and see ESI†). In addition, substrates, difficult to hydrogenate with included (see entries 1, 2 and 6 in Table 1).3 For entries 1–5 efficient

This journal is © The Royal Society of Chemistry 2018 Chem. Commun., 2018, 54, 13798--13801 | 13799

ChemComm
Published on 26 November 2018. Downloaded by University of Edinburgh on 1/21/2019 11:53:25 AM.
Chart 1 Proposed catalytic cycle for the hydrogenation of olefins using
pre-catalyst 2a-H.
hydrogenation is achieved, and for substrates 6–8 improved
conversions compared to [(P-P)Co(CH2SiMe3)2] are realised.3
In contrast to [(dppe)Co(CH2SiMe3)2],3 full hydrogenation of
cyclooctadiene (COD) to cyclooctane is realised within 6 h with
only 0.5 mol% loading of 2a-H. Nevertheless, the first hydro-
genation step of COD to yield cyclooctene (COE) is significantly
slower than the second one, and only after complete consump-
tion of COD rapid hydrogenation of COE occurs. This observa-
tion is consistent with the formation of a relatively stable COD
adduct, which hampers further hydrogenation and acts as a
dormant species outside the catalytic cycle (Chart 1). However,
after complete substrate consumption, cobalt particles form in
the reaction mixture.
To exclude heterogeneous hydrogenation, poisoning experi-
ments are required.12,42,43 For this purpose mercury is frequently
employed, since Hg covers the metal particle surface, which
reduces the catalytic activity, but this process may require a
significant induction period. An alternative and complementary
approach represents the addition of dibenzo[a,e]cyclooctatetraene
(DCT), that binds efficiently to homogeneous catalysts and stops
catalytic activity with no or only a very short induction period.42
Hg addition to 2a-H under an inert atmosphere (N2) induces no
degradation, but in the presence of Hg and H2 the catalytic
efficiency in COD hydrogenation is significantly reduced. While
this observation may imply heterogeneous catalysis, we instead
suggest that the catalytically active (homogeneous) species formed
after H2 addition to 2a-H is sensitive to Hg (Chart 1).44 In our
proposed mechanism the highly reactive [(NHC)CoH2] species is
formed, which readily undergoes olefin insertion and reductive
elimination to yield [(NHC)Co], which can either coordinate
olefins or undergo H2 addition (Chart 1).
We also noted that when 2a-H is exposed to H2 in the absence
of olefins rapid decomposition to cobalt particles occurs,
but these particles are not active in olefin hydrogenations.
Nevertheless, DCT as strongly chelating ligand efficiently shifts
the equilibrium to the catalytically inactive [(ItBu)Co(Z4-dct)]
species. Indeed, when DCT (6 equiv.) was added to reaction
mixture containing COD prior to H2 addition negligible conver-
sions to COE are observed, whereas the addition of DCT (6 equiv.)
13800 | Chem. Commun., 2018, 54, 13798--13801
View Article Online
Communication
Fig. 3 Poisoning studies performed with pre-catalyst 2a-H in the hydro-
genation of COD by addition of dct (6 equiv.). Lines are only drawn as
visual guides.
after 40 min of COD hydrogenation effectively stops the cata-
lytic activity (Fig. 3). In analogy to [(dppe)Co(Z4-cod)],3 we
assume that upon addition of DCT under catalytic conditions
[(ItBu)Co(Z4-dct)] is formed, but despite repeated attempts we
have so far been unable to isolate this species.
Nevertheless, the reactions of the difficult to hydrogenate
substrates (entries 7 and 8 in Table 1) were also probed and in
these cases adduct formation was established by EPR spectro-
scopy (see ESI† for details), which further strengthens our
proposed reaction mechanism (Chart 1). In both cases a spin-
state change from S = 3/2 to S = 1/2 is observed. Furthermore,
for tolane (PhCCPh) the corresponding bis(alkyne) complex
[(ItBu)Co(Z2-PhCCPh)2] (5) was isolated (Scheme 3), which
adopts a low-spin (S = 1/2) configuration with meff (300 K) =
2.38 mB (Fig. 1 and see ESI†).
The characteristic CC bond distance of the coordinated
alkyne (1.282(2) Å) in 5 (Fig. 2) is moderately elongated relative
to the CRC bond distance in diphenylacetylene (1.210(3) Å)45
approaching the value of a typical CC double bond (1.331 Å),46
which is consistent with p-backbonding from the Co atom into
the p*-orbitals of the coordinated alkyne. No reactivity of
complex 5 was observed upon addition of H2 in the presence
or absence of COD, establishing that 5 is not a catalytically
active species.
In conclusion, we demonstrated that the four-coordinated
[(tmeda)CoR2] (1a–c) compounds are excellent starting materials for
ligand substitution reactions with NHCs or bidenate phosphines.
Furthermore, the three-coordinate complex [(ItBu)Co(CH2SiMe3)2]
(2a-H) serves as a good homogeneous olefin hydrogenation pre-
catalyst showing superior activity to the four-coordinate com-
pound [(dppe)Co(CH2SiMe3)2]. Reaction of 2a-H with PhCCPh
Scheme 3 Preparation of complex 5.
This journal is © The Royal Society of Chemistry 2018

Communication
in the presence of H2 allowed the unusual paramagnetic cobalt
bis(alkyne) complex [(ItBu)Co(Z2-PhCCPh)2] (5) to be isolated
and structurally characterised. However, complex 5 is inactive
in olefin hydrogenation reactions, which rationalises the low
conversions observed in tolane hydrogenations.
We acknowledge the financial support by the Deutsche
Forschungsgemeinschaft (DFG) through the Heisenberg program
(WA 2513/6 und WA 2513/8) (MDW) and the Lower-Saxonian
Published on 26 November 2018. Downloaded by University of Edinburgh on 1/21/2019 11:53:25 AM.
graduate student program Catalysis for Sustainable Synthesis
(CaSuS) for a PhD fellowship (AE). Furthermore, we thank Prof.
M. Bröring (Institut für Anorganische und Analytische Chemie) at
the TU Braunschweig for access to the SQUID magnetometer and
X-band EPR spectrometer.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1 Catalysis Without Precious Metals, ed. R. M. Bullock, Wiley-VCH,
Weinheim, 2010.
2 J. A. Przyojski, H. D. Arman and Z. J. Tonzetich, Organometallics,
2013, 32, 723–732.
3 M. R. Friedfeld, G. W. Margulieux, B. A. Schaefer and P. J. Chirik,
J. Am. Chem. Soc., 2014, 136, 13178–13181.
4 P. J. Chirik, Acc. Chem. Res., 2015, 48, 1687–1695.
5 J. R. Dunetz, D. Fandrick and H.-J. Federsel, Org. Process Res. Dev.,
2015, 19, 1325–1326.
6 J. Sun and L. Deng, ACS Catal., 2016, 6, 290–300.
7 S. Krautwald, M. J. Bezdek and P. J. Chirik, J. Am. Chem. Soc., 2017,
139, 3868–3875.
8 Y. Liu and L. Deng, J. Am. Chem. Soc., 2017, 139, 1798–1801.
9 M. R. Friedfeld, H. Zhong, R. T. Ruck, M. Shevlin and P. J. Chirik,
Science, 2018, 360, 888–893.
10 G. R. Morello, H. Zhong, P. J. Chirik and K. H. Hopmann, Chem. Sci.,
2018, 9, 4977–4982.
11 M. R. Friedfeld, M. Shevlin, G. W. Margulieux, L.-C. Campeau and
P. J. Chirik, J. Am. Chem. Soc., 2016, 138, 3314–3324.
12 P. Bueschelberger, D. Gaertner, E. Reyes-Rodriguez, F. Kreyenschmidt,
K. Koszinowski, A. Jacobi von Wangelin and R. Wolf, Chem. – Eur. J.,
2017, 23, 3139–3151.
13 W. A. Herrmann and C. Köcher, Angew. Chem., Int. Ed. Engl., 1997,
36, 2162–2187.
14 F. E. Hahn and M. C. Jahnke, Angew. Chem., Int. Ed., 2008, 47, 3122–3172.
15 N-Heterocyclic Carbenes: From Laboratory Curiosities to Efficient
Synthetic Tools, ed. S. Dı́ez-González, RSC, Cambridge, 2011.
16 D. Bezier, J.-B. Sortais and C. Darcel, Adv. Synth. Catal., 2013, 355,
19–33.
17 M. N. Hopkinson, C. Richter, M. Schedler and F. Glorius, Nature,
2014, 510, 485–496.
This journal is © The Royal Society of Chemistry 2018
View Article Online
ChemComm
18 Z. Mo, Y. Liu and L. Deng, Angew. Chem., Int. Ed., 2013, 52,
10845–10849.
19 Z. Mo, J. Xiao, Y. Gao and L. Deng, J. Am. Chem. Soc., 2014, 136,
17414–17417.
20 Y. Gao, G. Li and L. Deng, J. Am. Chem. Soc., 2018, 140, 2239–2250.
21 J. Sun, L. Luo, Y. Luo and L. Deng, Angew. Chem., Int. Ed., 2017, 56,
2720–2724.
22 J. Sun, Y. Gao and L. Deng, Inorg. Chem., 2017, 56, 10775–10784.
23 J. Sun, C. Ou, C. Wang, M. Uchiyama and L. Deng, Organometallics,
2015, 34, 1546–1551.
24 L. Zhang, Y. Liu and L. Deng, J. Am. Chem. Soc., 2014, 136, 15525–15528.
25 J. Du, L. Wang, M. Xie and L. Deng, Angew. Chem., Int. Ed., 2015, 54,
12640–12644.
26 X.-N. Yao, J.-Z. Du, Y.-Q. Zhang, X.-B. Leng, M.-W. Yang, S.-D. Jiang,
Z.-X. Wang, Z.-W. Ouyang, L. Deng, B.-W. Wang and S. Gao, J. Am.
Chem. Soc., 2017, 139, 373–380.
27 D. Zhu, F. F. B. J. Janssen and P. H. M. Budzelaar, Organometallics,
2010, 29, 1897–1908.
28 R. E. Colborn, M. F. Garbauskas and C. I. Hejna, Inorg. Chem., 1988,
27, 3661–3663.
29 R. A. Andersen and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1977,
809–811.
30 R. A. Andersen and G. Wilkinson, Inorg. Synth., 1979, 19, 262–264.
31 R. S. Hay-Motherwell, G. Wilkinson, B. Hussain and M. B. Hursthouse,
Polyhedron, 1990, 9, 931–937.
32 W. Huang, T. Liu, D. Wu, J. Cheng, Z. W. Ouyang and C. Duan,
Dalton Trans., 2013, 42, 15326–15331.
33 T. E. Iannuzzi, Y. Gao, T. M. Baker, L. Deng and M. L. Neidig, Dalton
Trans., 2017, 46, 13290–13299.
34 S. Vaidya, S. K. Singh, P. Shukla, K. Ansari, G. Rajaraman and
M. Shanmugam, Chem. – Eur. J., 2017, 23, 9546–9559.
35 M. Craven, M. H. Nygaard, J. M. Zadrozny, J. R. Long and
J. Overgaard, Inorg. Chem., 2018, 57, 6913–6920.
36 A. K. Mondal, M. Sundararajan and S. Konar, Dalton Trans., 2018,
47, 3745–3754.
37 A. F. Orchard, Magnetochemistry, Oxford University Press, Oxford, 2003.
38 A. M. Bryan, G. J. Long, F. Grandjean and P. P. Power, Inorg. Chem.,
2013, 52, 12152–12160.
39 M. H. Al-Afyouni, E. Suturina, S. Pathak, M. Atanasov, E. Bill,
D. E. DeRosha, W. W. Brennessel, F. Neese and P. L. Holland,
J. Am. Chem. Soc., 2015, 137, 10689–10699.
40 A. Massard, P. Braunstein, A. A. Danopoulos, S. Choua and P. Rabu,
Organometallics, 2015, 34, 2429–2438.
41 E. A. Suturina, J. Nehrkorn, J. M. Zadrozny, J. Liu, M. Atanasov,
T. Weyhermueller, D. Maganas, S. Hill, A. Schnegg, E. Bill, J. R. Long
and F. Neese, Inorg. Chem., 2017, 56, 3102–3118.
42 D. R. Anton and R. H. Crabtree, Organometallics, 1983, 2, 855–859.
43 G. M. Whitesides, M. Hackett, R. L. Brainard, J. P. P. M. Lavalleye,
A. F. Sowinski, A. N. Izumi, S. S. Moore, D. W. Brown and
E. M. Staudt, Organometallics, 1985, 4, 1819–1830.
44 O. N. Gorunova, I. M. Novitskiy, Y. K. Grishin, I. P. Gloriozov,
V. A. Roznyatovsky, V. N. Khrustalev, K. A. Kochetkov and
V. V. Dunina, Organometallics, 2018, 37, 2842–2858.
45 I. E. Zanin, M. Y. Antipin and Y. T. Struchkov, Kristallografiya, 1991,
36, 411–419.
46 F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen and
R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1–S19.
Chem. Commun., 2018, 54, 13798--13801 | 13801