Organometallics
Article
J = 7.9 Hz, 1H, ph), 6.54 (d, J = 7.9 Hz, 2H, ph), 2.70−2.51 (m, 4H,
was then filtered through a PTFE syringe filter, diluted with Et O (4
2
CH), 1.47 (app. q, J = 7.6 Hz, 6H, CH ), 1.18 (app. q, J = 7.0 Hz, 6H,
mL), and a solution of HCl in Et O was added dropwise until the
3
2
CH ), 1.11 (app q, J = 6.9 Hz, 6H, CH ), 1.01 (q, J = 6.9 Hz, 6H, CH ).
precipitation of the hydrochloride was complete. The obtained
3
3
3
13
1
C{ H} NMR (101 MHz, δ, CD Cl ) 169.9 (t, J = 8.1 Hz), 127.5 (s),
ammonium salts were washed with Et
analyzed by H NMR spectroscopy.
2
O, dried under vacuum, and
2
2
1
1
1
05.6 (t, J = 5.5 Hz), 30.2 (t, J = 8.3 Hz), 29.3 (t, J = 11.6 Hz), 17.7 (s),
3
1
1
6.4 (s), 16.3 (t, J = 2.7 Hz), 16.1 (s). P{ H} NMR (162 MHz, δ,
1953237 (2a, 3a, 3b)) were collected at T = 100 or 150 K in a dry
stream of nitrogen on a Bruker Kappa APEX II diffractometer system
using graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å)
and fine sliced φ- and ω-scans. Data were reduced to intensity values
with SAINT and an absorption correction was applied with the
−
1
+
CD Cl ) 198.9. IR (ATR, cm ) 1650 (ν ). HR-MS (ESI , CH OH)
m/z calcd for C H CoNO P [M−Cl] 430.1111 found 430.1124.
2
2
NO
3
+
18
31
3 2
CH2
[
Co(PCP -iPr)(NO)Br] (2c). A solution of 1c (30 mg, 0.06 mmol) in
5
mL of pentane reacted with nitric oxide whereupon the color changed
from yellow to green. The obtained solution was filtered via syringe
filter and the solvent was removed in vacuum. Yield: 29 mg (91%). H
1
21
NMR (400 MHz, δ, CD Cl ) 7.00 (t, J = 7.4 Hz, 2H, ph), 6.92 (d, J =
multiscan approach implemented in SADABS. The structures were
2
2
22
8
.9 Hz, 1H, ph), 3.39 (t, J = 3.8 Hz, 1H, CH ), 3.35 (t, J = 3.8 Hz, 1H,
solved by the dual space method implemented in SHELXT and
23
2
2
refined against F with SHELXL. Non-hydrogen atoms were refined
with anisotropic displacement parameters. The H atoms were placed in
calculated positions and thereafter refined as riding on the parent
atoms. The Co−N and N−O distances of the minor (3%) orientation
of a disordered NO ligand were restrained to 1.74(2) and 1.16(2) Å,
respectively. Molecular graphics were generated with the program
CH ), 3.21 (t, J = 4.7 Hz, 1H, CH ), 4.17 (t, J = 5.5 Hz, 1H, CH ),
2
2
2
2
.60−2.44 (m, 4H, CH), 1.34 (app. q, J = 7.1 Hz, 6H, CH ), 1.06 (app.
3
13 1
q, J = 7.0 Hz, 6H, CH ), 1.03−0.92 (m, 12H, CH ). C{ H} NMR
3
3
(
101 MHz, δ, CD Cl ) 149.7 (t, J = 9.9 Hz), 124.5 (s), 122.3 (t, J = 8.1
2 2
Hz), 31.3 (t, J = 13.0 Hz), 25.6 (t, J = 9.7 Hz), 24.3 (t, J = 10.5 Hz), 10.1
3
1
1
(
7
s), 18.1 (s), 17.6 (s), 17.2 (s). P{ H} NMR (162 MHz, δ, CD Cl )
2 2
24
−
1
+
MERCURY.
Computational Details. The Amsterdam Density Functional
7.4. IR (ATR, cm ) 1639 (ν ). HR-MS (ESI , CH OH) m/z calcd
NO 3
+
for C H CoNOP [M−Br] 426.1526 found 426.1529.
20
35
2
2
5
NMe
program (ADF) was used in the Density Functional Theory
[
Co(PCP -iPr)(NO)]BF (3a). Method A. To a solution of 2a (80
4
26
calculations. Geometries were optimized without symmetry con-
straints, considering solvent (acetonitrile), with gradient correction,
mg, 0.16 mmol) in CH Cl (6 mL), AgBF (33 mg, 0.16 mmol) was
2
2
4
added and the mixture was stirred for 2 h at room temperature.
Insoluble materials were removed by filtration through a syringe filter
and the solvent was removed under reduced pressure. The remaining
red solid was washed twice with pentane (3 mL) and dried under a
27
using the Vosko−Wilk−Nusair Local Density Approximation of the
correlation energy and the Generalized Gradient Approximation with
28
29
Becke’s exchange and Perdew’s correlation functionals. Unre-
stricted calculations were carried out for open shell complexes. The
solvent correction was taken into account using the COSMO approach
implemented in ADF. Relativistic effects were treated with the ZORA
vacuum. Yield: 75 mg (85%). Method B. To a solution of
NMe
[
Co(PCP -iPr)(CO) ] (4a) (40 mg, 0.08 mmol) in CH Cl (3
2
2
2
mL), NOBF (10 mg, 0.08 mmol) was added and the reaction mixture
4
30
approximation. Triple ζ Slater-type orbitals (STO) were used to
describe all the valence electrons of H, C, B, and N, augmented with a
set of two polarization functions (H, single ζ 2s, 2p, C, N, O, and P
single ζ, 3d, 4f, and Co single ζ, 4p, 4f) and with a frozen core (1s) for C,
O, N, and P, and for Co (1s 2p). Orbitals and three-dimensional
was stirred for 30 min at room temperature whereupon the color
changed from yellow to dark red. All volatiles were removed under
reduced pressure; the product was washed with pentane (3 mL) and
1
dried under a vacuum. Yield: 39 mg (88%). H NMR (400 MHz, δ,
CD Cl ) 6.97 (t, J = 8.2 Hz, 1H, ph), 5.91 (d, J = 8.1 Hz, 2H, ph), 3.57−
2
2
31
structures were drawn with Chemcraft.
3
7
.38 (m, 4H, CH), 3.28 (app. t, J = 3.3 Hz, 6H, CH ) 1.52 (app. q, J =
3
1
3
1
.4 Hz, 12H, CH ), 1.45 (app. q, J = 7.6 Hz, 12H, CH ). C{ H} NMR
3
3
(
(
101 MHz, δ, CD Cl ) 164.0 (s), 135.9 (s), 102.1 (t, J = 6.6 Hz), 33.4
ASSOCIATED CONTENT
sı Supporting Information
2
2
■
3
1
1
s) 29.6 (t, J = 13.6 Hz), 18.9 (d, J = 11.7 Hz). P{ H} NMR (162
*
−
1
+
MHz, δ, CD Cl ) 156.0. IR (ATR, cm ) 1806 (ν ) HR-MS (ESI ,
2
2
NO
CH OH) m/z calcd for C H CoN OP [M]+ 456.1744 found
3
20 37
3
2
4
56.1736.
O
[Co(PCP -iPr)(NO)]PF6 (3b). This complex was prepared analo-
1
13
1
31
1
H, C{ H}, and P{ H} NMR spectra of all complexes
gously to 3a (method A) with 2b (50 mg, 0.11 mmol) and TlPF (39
mg, 0.11 mmol) as starting materials. Yield: 41 mg (75%). H NMR
6
and organic products (PDF)
1
Optimized Cartesian coordinates for DFT-calculated
(
400 MHz, δ, CD Cl ) 7.16 (t, J = 8.1 Hz, 1H, ph), 6.58 (d, J = 8.1 Hz,
2 2
2
1
H, ph), 3.79−3.26 (m, 4H, CH), 1.58 (app. q, J = 7.6 Hz, 12H, CH ),
13 1
3
.49 (app. q, J = 8.9 Hz, 12H, CH ). C{ H} NMR (101 MHz, δ,
3
CD Cl ) 170.5 (s), 137.6 (s), 106.8 (t, J = 6.8 Hz), 31.8 (t, J = 12.8 Hz),
1
(
2
2
31
1
8.0 (s), 17.5 (s). P{ H} NMR (162 MHz, δ, CD Cl ) 216.9. IR
ATR, cm ) 1861 (ν ). HR-MS (ESI , CH OH) m/z calcd for
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
2
2
−
1
+
NO 3
+
C H CoNO P [M] 430.1111 found 430.1110.
18
31
3 2
Reaction of 3a with LiCl. Formation of 2a. To a solution of 3a
15 mg, 0.03 mmol) in methanol-d (1 mL), LiCl (in excess) was added
(
4
and the suspension stirred for 10 min. The mixture was filtrated via
syringe filter into an NMR tube and spectra were immediately measured
revealing the quantitative formation of 2a. H, P{ H} NMR and ESI-
MS spectra were identical to those of 2a.
1
31
1
Corresponding Author
■
Reaction of 3a with CO. Formation of [Co(PCPNMe-iPr)(CO)-
+
(NO)] (5). CO (2 atm) was injected into the headspace of a solution of
3
a (15 mg) in CD Cl whereupon the color changed from magenta to
2 2
brown. The new compound is inherently unstable and decomposes
rapidly when the CO atmosphere is removed. Alternatively, the same
compound can be prepared by a solid−gas reaction. IR (ATR, cm )
1
−
1
Authors
732 (ν ), 2025 (ν ).
NO
CO
Jan Pecak − Institute of Applied Synthetic Chemistry, Vienna
General Procedure for the Hydroboration of Nitriles. The
University of Technology, A-1060 Vienna, Austria
Wolfgang Eder − Institute of Applied Synthetic Chemistry, Vienna
University of Technology, A-1060 Vienna, Austria
nitrile substrates (0.33 mmol, 1 equiv), nitrosyl complex 3a (4 mol %),
and pinacolborane (HBpin, 2.2 equiv) were mixed with 1 mL of
benzene and stirred at room temperature for 24 h. The reaction mixture
F
Organometallics XXXX, XXX, XXX−XXX