Q. Knijnenburg, D. Hetterscheid, T. M. Kooistra, P. H. M. Budzelaar
FULL PAPER
3
in 5 mL of hexane. An immediate colour change to green was ob-
served. After 2 h the mixture was filtered, and the filtrate was eva-
porated to dryness, yielding a green powder (yield not determined).
(t, JH,H ϭ 7.3 Hz, 2 H, Bz Hm), 6.65 (m, 1 H, Bz Hp), 5.59 (d,
3JH,H ϭ 6.9 Hz, 2 H, Bz Ho), 3.69 (d, JRhH ϭ 2.6 Hz, 2 H,
2
RhCH2), 3.17 (sept., 4 H, 3JH,H ϭ 6.8 Hz, CHMe2), 1.01Ϫ0.92 (m,
1H NMR (200 MHz, C6D6): δ ϭ 9.91 (t, JH,H ϭ 8 Hz, 1 H, Py 30 H, NϭCMe, CHMe2) ppm. 13C NMR (C6D6 75 MHz): δ ϭ
3
Hγ) ppm. The rest of the peaks could not be unambiguously as-
signed. The addition of H2 to the NMR sample resulted in disap-
166.8 (d, 2JRhC ϭ 2.3 Hz, NϭC), 156.2 (d, 2JRhC ϭ 2.9 Hz, Py Cα),
2
151.9 (d, JRhC ϭ 1.7 Hz, Bz Ci), 148.4 (dipp Ci), 141.0 (Py Cγ),
1
pearance of all the complex-related H NMR signals.
140.6 (dipp Co), 127.3 (Bz Co), 127.0 (Bz Cm), 126.5 (dipp Cp),
124.2 (dipp Cm), 123.6 (Py Cβ), 119.6 (Bz Cp), 28.6 (CHMe2), 24.0
and 23.8 (CHMe2), 19.5 (d, JRhC ϭ 1.7 Hz, NϭCMe) ppm. The
[Lhex,MeCoICH2SiMe3]: A 1 solution of LiCH2SiMe3 (1.6 mL,
1.60 mmol, 2.0 equiv.) in pentane and 8 mL of hexane were added
to [Lhex,MeCoIICl2] (0.45 g, 0.79 mmol). The mixture was stirred for
one hour, after which it was filtered. The filtrate was evaporated to
dryness, yielding 0.153 g of [Lhex,MeCoICH2SiMe3] (33.8%) as a
thick dark-red oil. 1H NMR (200 MHz, C6D6): δ ϭ 9.72 (t, 3JH,H ϭ
7.6 Hz, 1 H, Py Hγ), 7.31 (d, JH,H ϭ 7.6 Hz, 2 H, Py Hβ), 5.19
(t, JH,H ϭ 7.6 Hz, 4 H, hex Hα), 2.22 (quint, JH,H ϭ 7.6 Hz, 4
H, hex Hβ), 1.54 (quint, JH,H ϭ 7.6 Hz, 4 H, hex Hγ), 1.22 (m, 8
H, hex Ηδ, ε), 0.82 (t, JH,H ϭ 7.2 Hz, 6 H, hex Hζ), 0.02 (s, 2 H,
3
RhCH2 signal was not detected.
[Ldipp,MeRhICH2SiMe3]: A 1.0 solution of LiCH2SiMe3 in pen-
tane (0.54 mL 0.54 mmol, 2 equiv.) and 4 mL of toluene were ad-
ded to [Ldipp,MeRhICl] (170 mg, 0.27 mmol, 1 equiv.). The mixture
was stirred for 24 h. The solvent was removed in vacuo, yielding a
green-brown powder. Hexane (5 mL) was added, the mixture was
filtered and the filtrate was evaporated to dryness, yielding
[Ldipp,MeRhICH2SiMe3] as a green powder. 1H NMR (C6D6,
3
3
3
3
3
3
CoCH2), Ϫ0.14 (s, 9 H, SiMe3), Ϫ0.18 (s, 6 H, NϭCMe) ppm. 13
C
300 MHz): δ ϭ 8.06 (t, JH,H ϭ 7.9 Hz, 1 H, Py Hγ), 7.24 (d,
3JH,H ϭ 8.1 Hz, 2 H, Py Hβ), 7.15Ϫ7.03 (m, 6 H, dipp Hm,p), 3.26
NMR (75 MHz, C6D6): 162.42 (NϭC), 152.18 (Py Cα), 122.50 (Py
Cβ), 114.01 (Py Cγ), 59.35 (hex Cα), 32.20 and 22.89 (hex Cδ, ε),
29.08 and 27.36 (hex Cβ, γ), 20.39 (NϭCMe), 14.21 (hex Cζ), 3.00
(SiMe3) ppm. The signal for CoCH2 was not found. The addition
of H2 to the 1H NMR sample resulted in a colour change from
3
2
(sept., JH,H ϭ 6.8 Hz, 4 H, CHMe2), 1.87 (d, JRh;H ϭ 2.2 Hz, 2
3
H, RhCH2), 1.28 and 0.97 (2 ϫ d, JH,H ϭ 6.6 Hz, 12 H each,
CHMe2), 0.86 (s, 6 H, NϭCMe), 0.29 (s, 9 H, SiMe3) ppm. 13C
NMR (C6D6 75 MHz): δ ϭ 165.8 (d, 2JRhC ϭ 0.9 Hz, NϭC), 156.3
2
1
(d, JRhC ϭ 3.2 Hz, Py Cα), 149.4 (dipp Ci), 141.1 (Py Cγ), 140.6
dark red to green-brown and a loss of all the complex-related H
(dipp Co), 126.7 (dipp Cp), 124.3 (dipp Cm), 123.6 (Py Cβ), 28.2
NMR signals.
3
(CHMe2), 24.5 and 24.3 (CHMe2), 19.9 (d, JRh,C ϭ 2.0 Hz,
[Loctadec,MeCoICH2SiMe3]:
A 1 solution of LiCH2SiMe3
1
NϭCMe), 6.7 (d, JRh,C ϭ 33.0 Hz, RhCH2), 4.0 (SiMe3) ppm.
(0.90 mL, 900 µmol, 2.45 equiv.) in pentane and 8 mL of hexane
were added to [Loctadec,MeCoIICl2] (0.292 g, 368 µmol). The mixture
was stirred for two hours, after which it was filtered, and the sol-
[1]
Selected examples of square-planar CoI complexes [all except
1
vent was removed in vacuo leaving a deep purple-red product. H
ref.[1f] with tetradentate and fairly rigid ligands]. Bis(salicylid-
eneiminato): [1a] F. Arena, C. Floriani, A. Chiesi-Villa, C. Gua-
stini, Inorg. Chem. 1986, 25, 4589. [1b] S. Gambarotta, F. Arena,
C. Floriani, P. F. Zanazzi, J. Am. Chem. Soc. 1982, 104, 5082.
NMR (400 MHz, C6D6): δ ϭ 9.71 (t, 3JH,H ϭ 7.6 Hz, 1 H, Py Hγ),
3
3
7.31 (d, JH,H ϭ 7.6 Hz, 2 H, Py Hβ), 5.21 (t, JH,H ϭ 7.6 Hz, 4
3
H, octadec Hα), 2.26 (quint, JH,H ϭ 7.6 Hz, 4 H, octadec Hβ),
1.59 (quint, JH,H ϭ 7.2 Hz, 4 H, octadec Hγ), 1.5Ϫ1.1 (m, 56 H,
[1c]
G. Fachinetti, C. Floriani, P. F. Zanazzi, A. R. Zanari, In-
3
[1d]
org. Chem. 1979, 18, 3469. Porphyrinato:
Fischer, R. Weiss, Inorg. Chem. 1984, 23, 2958. Phthalocyanin-
P. Doppelt, J.
octadec ΗδϪρ) ppm. octadec Hꢀ is presumably obscured by the
resonance of traces of hexane. The signals for CoCH2, SiMe3 and
NϭCMe could not be unambiguously assigned.
[1e]
ato:
1998, 624, 715. Bis(imino)succinonitrile:
Liaw, Y. Wang, A. Simon, Angew. Chem. Int. Ed. Engl. 1985,
H. Huckstadt, H. Homborg, Z. Anorg. Allg. Chem.
[1f]
S.-M. Peng, D.-S.
[Ldipp,MeRhICH3]: Toluene (2 mL) was added to a mixture of
[Ldipp,MeRhICl] (100 mg, 0.16 mmol) and MeLi (7.1 mg,
0.32 mmol, 2 equiv.) and the reaction mixture was stirred for three
days. The obtained product was filtered off and the filtrate was
evaporated to dryness, yielding 91 mg of [Ldipp,MeRhICH3] (84%)
as a dark green solid. 1H NMR (300 MHz, C6D6): δ ϭ 8.19 (t,
[1g]
24, 210. Miscellaneous:
Y.-S. You, G.-H. Lee, S.-M. Peng,
J. Chin. Chem. Soc. (Taipei) 1996, 43, 261.
[2]
CoI is more often tetrahedral. Selected examples (without li-
[2a]
gand constraints): L4Coϩ:
N. Lu, N. C. Norman, A. G.
Orpen, M. J. Quayle, P. L. Timms, G. R. Whittell, J. Chem.
[2b]
Soc., Dalton Trans. 2000, 4032. [L3CoCl]:
R. A. Jones, A.
L. Stuart, J. L. Atwood, W. E. Hunter, J. Crystallogr. Spectrosc.
3
3JH,H ϭ 7.9 Hz, 1 H, Py Hγ), 7.34 (d, JH,H ϭ 7.7 Hz, 2 H, Py
Res. 1983, 13, 273. One of the few examples with nitrogen do-
3
Hβ), 7.22Ϫ7.10 (m, 6 H, dipp Hm,p), 3.19 (sept., 4 H, JH,H
ϭ
[2c]
nors is [(tpz)Co(CO)]:
J. L. Detrich, R. Konecny, W. M.
2
6.8 Hz, CHMe2), 2.12 (d, JRhH ϭ 1.1 Hz, 3 H, RhMe), 0.99 (m,
Vetter, D. Doren, A. L. Rheingold, K. H. Theopold, J. Am.
Chem. Soc. 1996, 118, 1703.
24 H, CHMe2), 0.73 (s, 6 H, NϭCMe) ppm. 13C NMR (75 MHz,
2
[3] [3a]
C6D6): δ ϭ 166.8 (NϭC), 155.3 (d, JRhC ϭ 2.7 Hz, Py Cα), 148.3
V. C. Gibson, M. Humphries, K. Tellmann, D. Wass, A. J.
P. White, D. J. Williams, Chem. Commun. 2001, 2252. [3b] T. M.
Kooistra, Q. Knijnenburg, J. M. M. Smits, A. D. Horton, P.
H. M. Budzelaar, A. W. Gal, Angew. Chem. Int. Ed. 2001, 40,
4719.
(dipp Ci), 140.6 (Py Cγ), 140.4 (dipp Co), 123.6 (dipp Cm), 123.1
(Py Cβ), 28.2 (CHMe2), 23.9 and 23.6 (CHMe2), 18.9 (NϭCMe),
1
1.2 (d, JRhC ϭ 21.0 Hz, RhMe) ppm. dipp Cp is presumably ob-
scured by the resonance of the C6D6 solvent.
[4]
[5]
S. Nuckel, P. Burger, Organometallics 2001, 20, 4345.
E. L. Dias, M. Brookhart, P. S. White, Organometallics 2000,
19, 4995.
P. Margl, L. Deng, T. Ziegler, Organometallics 1999, 18, 5701.
B. de Bruin, E. Bill, E. Bothe, T. Weyhermuller, K. Wieghardt,
Inorg. Chem. 2000, 39, 2936.
P. H. M. Budzelaar, B. de Bruin, A. W. Gal, K. Wieghardt, J.
H. Van Lenthe, Inorg. Chem. 2001, 40, 4649.
N.-E. Andersson, T. O. Soine, J. Am. Pharm. Ass. 1950, 39, 463.
Burger reported that non-planar structures also form easily for
Rh and Ir and are sometimes even preferred.[4] However, in
[Ldipp,MeRhIBz]: Toluene (2 mL) was added to a mixture of
[Ldipp,MeRhICl] (100 mg, 0.27 mmol) and Bz2Mg (41 mg,
0.27 mmol, 1 equiv.). The mixture was stirred for 24 h. The mag-
nesium salts were separated from the reaction products by filtration
and the filtrate was evaporated to dryness, yielding a purple pow-
der. Hexane (5 mL) was added, the mixture was filtered and the
filtrate was evaporated to dryness, yielding [Ldipp,MeRhIBz] as a
[6]
[7]
[8]
[9]
1
3
[10]
purple powder. H NMR (C6D6, 200 MHz): δ ϭ 7.97 (t, JH,H
ϭ
7.9 Hz, 1 H, Py Hγ), 7.31Ϫ7.17 (m, 8 H, dipp Hm,p, Py Hβ), 7.21
1210
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2004, 1204Ϫ1211