Terminal cobalt(III) imido complexes supported by tris(carbene) ligands: Imido insertion into the cobalt-carbene bond

Article abstract of DOI:10.1021/ja044271b

Highly reactive tris-carbene Co(I) complexes [(TIMEN^aryl)Co]Cl react with organic azides to yield monomeric Co(III) imido complexes [(TIMEN^aryl)Co(NAr-)](BPh₄) (aryl = mes, xyl; Ar = -C₆H₄-CH₃, -C₆H₄-OCH₃). The cobalt-imido fragment in these complexes is electrophilic and, as a result, the imido group readily inserts into the cobalt-carbene bond, yielding bis-carbene imine cobalt complexes. Copyright

Full text of DOI:10.1021/ja044271b

Published on Web 11/25/2004
Terminal Cobalt(III) Imido Complexes Supported by Tris(Carbene) Ligands:
Imido Insertion into the Cobalt-Carbene Bond
Xile Hu and Karsten Meyer*
Department of Chemistry and Biochemistry, UniVersity of California, San Diego, 9500 Gilman DriVe,
MC 0358, La Jolla, California 92093-0359
Received September 20, 2004; E-mail: kmeyer@ucsd.edu
Scheme 1
Transition metal imido species have attracted much attention due
to their postulated roles in catalysis and their potential in N-atom
transfer chemistry.1,2 Late-transition metal imido complexes, how-
ever, are rare, which is likely due to mismatched reactivity of the
hard imido ligand and the soft electron-rich metal center.3-7 For
about 10 years, Bergman’s iridium derivatives of the general
formula [(Cp*)IrtNR] (R ) aryl, alkyl, silyl) represented the only
structurally characterized late-metal complexes bearing a terminal
imido functionality.3 More recently, the work of Hillhouse and
Mindiola on [(dtbpe)Ni(N(2,6-(CHMe2)2C6H3))] (dtbpe ) 1,2-bis-
(di-tert-butylphosphino)ethane) revived this field of research and
demonstrated that late first-row metal imido complexes are acces-
sible by employing electron-rich bulky ancillary ligands.4 Soon after,
Peters et al. prepared the first mononuclear Co(III) and Fe(III) imido
complexes via oxidative nitrene transfer to a Co(I) and Fe(I) tris-
(phosphine) species.5,6 Following similar strategies, Theopold et
al. and Warren et al. synthesized transient and stable Co(III) imido
complexes supported by tris(pyrazolyl)borate and â-diketiminate
ligands.8,9
In our quest to develop tripodal N-heterocyclic carbene com-
plexes for small molecule activation, we recently synthesized the
Co(I) tris(carbene) complex [(TIMENxyl)Co]Cl (1a, TIMEN ) tris-
[2-(3-arylimidazol-2-ylidene)ethyl]amine, xyl ) 2,6-dimethylphen-
The Co-Nimido distance of 1.675(2) Å compares well with that
yl)10 that reacts with a variety of small molecules. For example,
of 1.624(4) and 1.658(2) Å in the only other two reported terminal
1a reacts with dioxygen to form a Co(III) peroxo species, which is
able to transfer a single oxygen atom to electrophilic organic
substrates.10 Herein we report the reaction of 1a and its mesitylene
analogue, [(TIMENmes)Co]Cl (1b), with aryl azides, yielding
monomeric Co(III) imido complexes. The cobalt-imido fragment
in these complexes is electrophilic, and as a result, the imido group
readily inserts into the cobalt-carbene bond. To the best of our
knowledge, this intramolecular imido insertion reaction has not been
observed before11 and thus reveals a new type of reactivity of this
interesting and valuable class of compounds.
Co(III) imido species.6,9 This short distance, together with an almost
linear Co-Nimido-CAr angle of 168.6(2)°, is indicative of strong
multiple bond character within the Co-NAr entity. The Nimido
-
C
aryl distance of 1.386(4) Å is significantly smaller than that of an
N-C single bond (sum of the N and C covalent radii is 1.52 Å),13
suggesting a substantial degree of electron delocalization within
In an initial attempt to prepare a Co(III) imido species, we treated
1a with trimethylsilyl azide. The reaction proceeds smoothly but
yields the one-electron oxidized azido species [(TIMENxyl)Co(N3)]-
Cl (2, 92% yield). However, reaction of 1a and 1b with aryl azides
at -35 °C produced the desired deep-green Co(III) imido complexes
[(TIMENR)Co(NArR′)]Cl (3a-4b, Scheme 1) that could be isolated
at low temperature in near quantitative yields. Complex 2 was fully
characterized, including paramagnetic 1H NMR, IR, UV-vis
spectroscopy, SQUID measurements, CHN analysis, and X-ray
crystallography.12 Complexes 3a-4b are diamagnetic (d6 low-spin,
S ) 0), and the 1H spectra suggest a C3-symmetry of these
molecules in solution. In the solid-state structure of 3b(BPh4),12
the TIMENmes ligand is coordinated in a tridentate fashion, rendering
the complex in a pseudotetrahedral geometry of three carbenoid
carbons and the imido nitrogen atom (Figure 1, left).
Figure 1. Solid-state molecular structures of 3b(BPh4) (left) and 5b(BPh4)2‚
1.5Et2O (right). Hydrogen atoms, counteranions, and solvent molecules
are omitted for clarity, thermal ellipsoids are shown at 50% probability.
Selected bond lengths (Å) and angles (deg): 3b: Co-C3 1.940(3), Co-
C17 1.938(3), Co-C31 1.962(3), Co-N8 1.675(2), N8-C43 1.386(4), Co-
N8-C43 168.6(2), Co-N1 4.01. 5b: Co-C3 2.043(2), Co-C17 2.019(2),
Co-N1 2.169(2), Co-N8 1.9973(19), N8-C31 1.330(3).
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C O M M U N I C A T I O N S
complexes. However, monitoring this reaction by UV-vis spec-
troscopy confirmed that the reaction follows first-order kinetics and
the rate-limiting step is indeed the imido insertion (Figures S8-
S11).12 The rates of these reactions are independent of the solvent
and were determined to be 1.6 × 10-4 (3a), 8.7 × 10-5 (3b), 3.4
× 10-4 (4a), and 3.0 × 10-4 s-1 (4b), respectively (at 20 °C). In
general, the insertion is faster for less electron-rich species,
suggesting that the reaction proceeds via an electrophilic attack of
the imido group on the Co-C bond.
As evidenced by these unusual intramolecular imido insertion
reactions,11 the highly electrophilic imido complexes 3a-4b are
distinctively different from other terminal cobalt(III) imido species.
The slightly nucleophilic tris(phosphine) cobalt imido complex
reacts slowly, for instance, with CO to form an isocyanate,6 and
the transient tris(pyrazolyl)borate cobalt imido species undergoes
intramolecular C-H activation to form a cobalt amide complex.8
It is noteworthy that reactions of 3a-4b with an excess of
nucleophiles, such as styrene and tetramethylimidazol-2-ylidene,
do not result in intermolecular imido transfer, proving the intramo-
lecular insertion reaction to be favored (faster). Our results support
the perspective of using well-defined late-metal imido complexes
as N-group transfer agents for nucleophilic organic substrates, such
as alkenes, in the absence of intramolecular reactive sites. Work is
currently underway to control the intramolecular insertion rates
while maintaining the electrophilicity of these imido species.
Figure 2. Representative frontier orbitals of model complex 3bm. (a) One
of the two π-antibonding orbitals, LUMO+1, with d(xz)/d(yz) parentage
and (b) HOMO-2 orbital showing interaction between carbene carbon (C3)
and imido nitrogen (N8).
the aryl imido ligand. Also notable is the short distance between
the imido nitrogen (N8) and one of the coordinated carbene carbon
(C3) ligands: the N8-C3 distance of 2.982 Å is considerably
smaller than the sum of their van der Waals radii (3.25 Å).13
To gain insight into the electronic structure of complexes 3a-
4b, DFT calculations (ADF 2003.1, ZORA/TZP, BP86) were
carried out on the model compound 3bm, in which the TIMEN
mesitylene substituents were replaced by methyl groups.12 The
calculation results in a core geometry that is in good agreement
with the experimentally determined structure of 3b(BPh4) (Figure
S5 and Table S1). In the orbital splitting diagram (Figure S7), the
Acknowledgment. We thank Ingrid Castro-Rodriguez and Prof.
Arnold L. Rheingold (UCSD) for help with the crystallography.
K.M. is an Alfred P. Sloan Research Fellow.
2
2
2
2
2
2
0
0
Co(III) ion adopts a d(xy) d(x -y ) d(z ) dxz dyz ground-state electron
configuration.12 Accordingly, the electronic structure of this cationic
cobalt(III) imido complex appears to be similar to that of the neutral
tris(phosphine) cobalt imido complex synthesized by Peters et al.6
As expected, MOs of dxz and dyz parentage are greatly destabilized
by strong π-bonding interaction with the imido π-lone pairs and
thus lie at highest energies (Figure 2a). The six d electrons occupy
Supporting Information Available: Experimental and spectro-
scopic details of new compounds, ORTEPs, and complete listings of
structural parameters for 2b(BPh4)‚CH3CN, 3b(BPh4), 5b(BPh4)2‚
1.5Et2O, and 6a(BPh4)2‚Et2O. This material is available free of charge
via the Internet at http://pubs.acs.org.
2
MOs up to the dz orbital, which is σ-antibonding with respect to
the Co-NR bond; the π* orbitals dxz and dyz remain unoccupied
(LUMOs). Although the metal-imido group is often formulated
as a triple bond, comprising two degenerate π- and one σ-type
orbital interactions,2 the bonding within the cobalt imido unit
reported here is best described as a formal double bond.14
Interestingly, the DFT study also suggests that there is a consider-
able amount of electron density donated from one of the σ-orbitals
of the carbenoid carbon into the π-orbital of the imido nitrogen
(Figure 2b). This finding correlates well with the short distance
between the C3 and N8 atom observed in the crystal structure and
the tendency of the imido group to insert into the Co-C bond in
solution.
Complexes 3a-4b are stable in solid state and in solution at
-35 °C. In solution at room temperature, however, the imido group
readily inserts into one of the cobalt-carbene bonds as established
by 1H NMR spectroscopy and X-ray crystallography. We propose
that the immediate product of the insertion reaction is a cobalt(I)
imine species, which further disproportionates to form cobalt(II)
imine complexes [(TIMENaryl)*Co]2+ (5a-6b), metallic cobalt(0)
species, and unidentified organic side products (Scheme 1). The
molecular structure of divalent 5b(BPh4)2‚1.5Et2O and 6a(BPh4)2‚
Et2O were determined and show isostructural geometries (5b,
Figure 1 right; 6a, Figure S13).12 The modified TIMEN* ligand
coordinates to the Co ion through two of its remaining carbenoid
carbons, the anchoring nitrogen and the newly formed imine N
atom. The disproportion rate is likely faster than that of the imido
insertion, thereby preventing the isolation of the cobalt(I) imine
References
(1) Groves, J. T.; Takahashi, T. J. Am. Chem. Soc. 1983, 105, 2073-2074.
Wigley, D. E. In Progress in Inorganic Chemistry; 1994; Vol. 42, pp
239-482. DuBois, J.; Tomooka, C. S.; Hong, J.; Carreira, E. M. Acc.
Chem. Res. 1997, 30, 364-372. Eikey, R. A.; Abu-Omar, M. M. Coord.
Chem. ReV. 2003, 243, 83-124.
(2) Nugent, W. A.; Mayer, J. M. Metal-Ligand Multiple Bonds; John Wiley
and Sons: New York, 1988.
(3) Glueck, D. S.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1989,
111, 2719-2721. Glueck, D. S.; Wu, J. X.; Hollander, F. J.; Bergman,
R. G. J. Am. Chem. Soc. 1991, 113, 2041-2054.
(4) Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc. 2001, 123, 4623-
4624. Mindiola, D. J.; Hillhouse, G. L. Chem. Commun. 2002, 1840-
1841.
(5) Brown, S. D.; Betley, T. A.; Peters, J. C. J. Am. Chem. Soc. 2003, 125,
322-323.
(6) Jenkins, D. M.; Betley, T. A.; Peters, J. C. J. Am. Chem. Soc. 2002, 124,
11238-11239.
(7) Au, S. M.; Huang, J. S.; Yu, W. Y.; Fung, W. H.; Che, C. M. J. Am.
Chem. Soc. 1999, 121, 9120-9132. Waterman, R.; Hillhouse, G. L. J.
Am. Chem. Soc. 2003, 125, 13350-13351.
(8) Thyagarajan, S.; Shay, D. T.; Incarvito, C. D.; Rheingold, A. L.; Theopold,
K. H. J. Am. Chem. Soc. 2003, 125, 4440-4441.
(9) Dai, X. L.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-
4799.
(10) Hu, X.; Castro-Rodriguez, I.; Meyer, K. J. Am. Chem. Soc. 2004, 126,
13464-13473.
(11) Nitrene insertions resulting from reactions of late-metal organometallic
complexes with organoazides were previously reported: Hessell, E. T.;
Jones, W. D. Organometallics 1992, 11, 1496-1505. Matsunaga, P. T.;
Hess, C. R.; Hillhouse, G. L. J. Am. Chem. Soc. 1994, 116, 3665-3666.
(12) See Supporting Information.
(13) Winter, M. WebElements; http://www.webelements.com.
(14) The net σ-bonding, resulting from interaction of the cobalt 4pz orbital
with the imido nitrogen sp hybrid orbital, is insignificant as the HOMO
2
contains only 8% Co 4pz but 52% Co 3dz orbital contribution.
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