1852
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
Polezhaev et al.
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzeneꢀ1ꢀyl}carbonylꢀ
rhodium(I), Rh(СО)[2,6ꢀ(But PO) C H ] (3). Complex 1
the beginning of the reaction as detected by NMR. The solution
was filtered through a celite layer, and then concentrated to
yield a yellowꢀbrown finelyꢀcrystalline powder. The 1Н NMR
and 31Р{1H} NMR spectra of the complex redissolved in C6D6
showed the decomposition products. 1Н NMR (400 MHz,
C6D6), δ: 6.99 (t, 1 H, 4ꢀС6H3, JH,H = 7.8 Hz); 6.89 (d, 2 Н,
3,5ꢀС6H3, JH,H = 7.8 Hz); 1.25 (virt. t, 36 H, But); –3.01 (br.d,
2 H, RhH2, JRh,H = 18.5 Hz). 31Р{1Н} NMR (161.98 MHz, C6D6),
δ: 216.0 (d, JRh,P = 165.56 Hz). 13C{1H} NMR (100.5 MHz,
C6D6), δ: 168.6 (t); 126.2 (s); 104.4 (t); 41.0 (t); 38.5 (t); 28.5
(t), T1 = 53 ms at 23 °С.
2
2
6
3
(20 mg, 0.037 mmol) was dissolved in CDCl3, placed in an
NMR tube, and treated by bubbling CO through the solution
for 10 min (therewith the solution color changed from brownꢀ
red to yellow). Product 3 was characterized by NMR. Then
the solvent was removed in vacuo to dryness to yield yellow
crystals (19.5 mg, 100%). 1Н NMR (400.13 MHz, CDCl3), δ:
6.80 (d, 2 Н, 3,5ꢀС6H3, JH,H = 8.8 Hz); 7.14 (t, 1 H, 4ꢀС6H3,
JH,H = 8.8 Hz); 1.34 (virt. t, 36 H, But). 31Р{1Н} NMR
(161.98 MHz, CDCl3), δ: 214.5 (d, JRh,P = 156.6 Hz).
13C{1H} NMR (100.5 MHz, CDCl3), δ: 201.3 (dt, JRh,C
= 30.0 Hz); 95.9 (t); 41.0 (t); 35.7 (t); 29.2 (d). IR (СHCl3):
СО 1961 cm–1. Found (%): С, 51.98; Н, 7.44. С23H39O3P2Rh.
=
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}(dioxygen)ꢀ
rhodium(I), Rh(О )[2,6ꢀ(But PO) C H ] (6). A solution of
2
2
2
6
3
ν
complex 10 in deuteriobenzene prepared as described above in
an NMR tube was frozen in liquid nitrogen, and then the
hydrogen atmosphere was removed by evacuation (oil pump),
after which the tube was refilled with gaseous oxygen to 1 atm.
The solution was warmedꢀup to room temperature and vigorously
shaken for 5 min. Its color changed from yellowꢀbrown to
emerald green. In attempting to isolate the complex by evaporaꢀ
tion of the solvent or crystallization, it decomposed to form a
black powder and ligand oxidation products. 1Н NMR (400 MHz,
C6D6), δ: 6.86 (t, 1 Н, 4ꢀС6H3, JH,H = 8.1 Hz); 6.68 (d, 2 H,
3,5ꢀС6H3, JH,H = 8.1 Hz); 1.44 (virt. t, 36 H, But). 31Р{1Н}
NMR (161.98 MHz, C6D6), δ: 193.7 (d, JRh,P = 157.6 Hz).
Calculated (%): C, 52.08; H, 7.36.
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}(acetonitrile)ꢀ
rhodium(I), Rh(CH3CN)[2,6ꢀ(But2PO)2C6H3] (4). A solution of
complex 1 (40 mg, 0.074 mmol) in acetonitrile (3 mL) was
prepared in a Schlenk vessel, and then sodium tertꢀbutoxide
(10 mg, 0.1 mmol) was added under argon. The reaction mixture
was stirred at room temperature for 3 h that was accompanied by
its color changing from brownꢀred to lemon yellow. The resulting
solution was filtered through a celite layer and then concentrated
in vacuo (oil pump). The product yellowꢀpale fineꢀcrystalline
powder was obtained in quantitative yield. 1Н NMR (400 MHz,
C6D6), δ: 7.07 (t, 1 Н, 4ꢀС6H3, JH,H = 6.2 Hz); 7.01 (d, 2 H,
3,5ꢀС6H3, JH,H = 6.2 Hz); 1.56 (virt. t, 36 H, But); 0.80 (s, 3 H,
СH3CN). 31Р{1Н} NMR (161.98 MHz, C6D6), δ: 194.2 (d,
IR (C6D6): ν 839 cm–1
.
О2
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}(deuteroꢀ
hydrogen)rhodium(I), Rh(НD)[2,6ꢀ(But PO) C H ] (10ꢀd ).
2
2
6
3
1
JRh,P = 179.6 Hz). IR (CH2Cl2): ν
2068 cm–1. Found (%):
A solution of complex 10 in C6D6 prepared as described above
in an NMR tube was frozen in liquid nitrogen, the hydrogen
atmosphere was removed by evacuation (oil pump), and then
the tube was refilled with gaseous deuterium to 1 atm. The
solution was warmedꢀup to room temperature and vigorously
СN
С, 52.98; Н, 7.85. С24H42NO2P2Rh. Calculated (%): C, 53.04;
H, 7.73.
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}(tetrahydroꢀ
thiophene)rhodium(I), Rh(S(CH ) )[2,6ꢀ(But PO) C H ] (5).
2
2 4
2
6
3
1
A solution of complex 1 (40 mg, 0.074 mmol) in tetrahydroꢀ
thiophene (3 mL) was prepared in a Schlenk vessel, then sodium
tertꢀbutoxide (10 mg, 0.1 mmol) was added under argon. The
reaction mixture was stirred at room temperature for 3 h; the
color changed from brownꢀred to yellowꢀbrown. The resulting
solution was filtered through the celite layer and then conꢀ
centrated in vacuo (oil pump). The product was isolated as a
yellowꢀbrown paste (yield 80%). 1Н NMR (400 MHz, C6D6), δ:
7.09 (t, 1 Н, 4ꢀС6H3, JH,H = 7.8 Hz); 6.97 (d, 2 H, 3,5ꢀС6H3,
JH,H = 7.8 Hz); 2.80 (m, 4 H, C4H8S); 1.65 (d, 2 H, C4H8S,
JH,H = 13.3 Hz); 1.50 (virt. t, 36 H, But); 1.25 (d, 2 H, C4H8S,
JH,H = 13.3 Hz). 31Р{1Н} NMR (161.98 MHz, C6D6), δ: 195.9
(d, JRh,P = 174.7 Hz). 13C{1H} NMR (100.5 MHz, C6D6), δ:
167.9 (t); 140.9 (dt, JRh,C = 30.0 Hz); 124.2 (s); 103.5 (t); 40.9
(s); 39.4 (m); 29.0 (d); 32.11 (s). Found (%): С, 52.60; Н, 8.10.
С26H47O2P2RhS. Calculated (%): C, 52.88; H, 7.97.
shaken for 5 min. Н NMR (400 MHz, C6D6), δ: 6.99 (t, 1 H,
4ꢀС6H3, JH,H = 7.8 Hz); 6.89 (d, 2 Н, 3,5ꢀС6H3, JH,H = 7.8 Hz);
1.25 (virt. t, 36 H, But); –3.01 (dt, 1 H, RhHD, JRh,H = 18.8 Hz,
JD,H = 38.8 Hz).
Reaction of Rh(Н )[2,6ꢀ(But PO) C H ] (10) with N .
2
2
2
6
3
2
Preparation of complexes Rh(N2)[2,6ꢀ(But PO)2C6H3] (11) and
2
[(2,6ꢀ(But2PO)2C6H3)Rh]2(N2) (12). A solution of complex 10
in C6D6 prepared as described above in an NMR tube was frozen
in liquid nitrogen, the hydrogen atmosphere was removed by
evacuation (oil pump), and then the tube was refilled with
gaseous nitrogen to 1 atm. The solution was warmed up to room
temperature and vigorously shaken for 5 min; then the hydrogen
atmosphere in the tube was repeatedly replaced with nitrogen.
The 31Р{1H} NMR spectrum had two doublets in a 1 : 1 ratio
assigned to complexes 11 and 12. The evaporation of the solvent
from the solution yielded brown powder containing only complex
12 and decomposition products.
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}(dihydrogen)ꢀ
rhodium(I), Rh(Н )[2,6ꢀ(But PO) C H ] (10). A solution of
{2,6ꢀBis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}(dinitrogen)ꢀ
rhodium(I) (11). 1Н NMR (400 MHz, C6D6), δ: 6.92 (t, 1 Н,
4ꢀС6H3, JH,H = 7.8 Hz); 6.80 (d, 2 H, 3,5ꢀС6H3, JH,H = 7.8 Hz);
1.37 (virt. t, 36 H, But). 31Р{1Н} NMR (161.98 MHz, C6D6), δ:
201.3 (d, JRh,P = 170.5 Hz). 13C{1H} NMR (100.5 MHz, C6D6),
δ: 169.30 (t, J = 8.7 Hz); 138.95 (dt, J = 9.7 Hz, J = 34.5 Hz);
126.18 (s), 104.44 (t, J = 6.7 Hz); 39.36 (td); 38.60 (t); 27.65 (t).
2
2
2
6
3
complex 1 (20 mg, 0.037 mmol) in C6D6 was prepared in a
J. Young NMR tube, which was then evacuated three times,
filled with hydrogen to atmospheric pressure, and vigorously
shaken for 5 min. The solution was frozen in liquid nitrogen,
then sodium tertꢀbutoxide (5 mg, 0.052 mmol) was added into
the tube. After the subsequent evacuation the tube was refilled
with hydrogen to 1 atm. The reaction mixture was warmed up to
room temperature and vigorously shaken for 15—20 min. The
solution color changed from redꢀbrown to yellowꢀbrown, and
white NaCl precipitated. Product 10 was formed in 30 min after
IR (C6D6): ν 2151 cm–1
.
N2
Di[{2,6ꢀbis[di(tertꢀbutyl)phosphinito]benzenꢀ1ꢀyl}rhodium(I)]ꢀ
(dinitrogen) (12). 1Н NMR (400 MHz, C6D6), δ: 6.89 (t, 1 Н,
4ꢀС6H3, JH,H = 7.8 Hz); 6.78 (d, 2 H, 3,5ꢀС6H3, JH,H = 7.8 Hz);