Multifunctional 2H-1,2-Azaphosphole Complexes
Organometallics, Vol. 22, No. 26, 2003 5433
F igu r e 4. Molecular structure of one of the two indepen-
dent molecules of 11d in the crystal (ellipsoids represent
50% probability levels; hydrogen atoms are omitted for
clarity). Selected bond lengths [Å] and angles [deg]: N2-
C12 1.344(2) 1.340(2)), N1-P1-C13 94.00(9) 93.94(8)),
N1-P1-C6 105.82(9) 105.10(9), C6-P1-C13 106.54(9)
106.06(9)), C12-N1-P1 110.80(13) 110.87(13)), C14-C13-
P1 107.37(14) 106.99(14)), C12-C14-C13 111.60(17)
112.51(17)), N1-C12-C14 115.47(16) 115.06(16).
F igu r e 2. Molecular structure of one of the two indepen-
dent molecules of 11b in the crystal (ellipsoids represent
30% probability levels; hydrogen atoms are omitted for
clarity). Selected bond lengths [Å] and angles [deg]: N2-
C13 1.345(3) (1.341(3)), N1-P1-C11 94.13(10) (94.32(10)),
N1-P1-C6 105.76(11) 105.17(11), C6-P1-C11 106.09(11)
108.01(11), C13-N1-P1 110.37(16) 110.30(16), C12-C11-
P1 107.01(17) (106.47(18)), C11-C12-C13 112.7(2)
(112.7(2)), N1-C13-C12 115.5(2) (115.5(2)).
solutions heated at 120 °C for 45 min with slow stirring. All
volatile components were removed in vacuo (ca. 0.01 mbar)
and the products separated by low-temperature column chro-
matography (SiO2, -10 °C, 10 × 2 cm, n-pentane/diethyl ether,
1:1). Evaporation of the second fractions yielded complexes
11a -d as yellow solids.
{[3,4-Bis(m eth oxyca r bon yl)-2-(2-cya n oeth yl)-5-(N-tr i-
p h en ylp h osp h on ioim in oyl)-2H -1,2-a za p h osp h ole-KP ]-
p en ta ca r bon yltu n gsten (0)} (11a ). Yield: 650 mg (78%); mp
1
152 °C (dec); H NMR (CDCl3) δ 1.51 (mc, 2H, CH2CH2CN),
2.23 (mc, 2H, CH2CH2CN), 3.77 (s, 3H, OCH3), 4.02 (s, 3H,
OCH3), 7.48 (mc, 7H, Ph), 7.58 (mc, 3H, Ph), 7.79 (mc, 5H, Ph);
2
13C{1H} NMR (CDCl3) δ 11.2 (d, J (P,C) ) 3.2 Hz, -CH2CH2-
1
CN), 30.8 (d, J (P,C) ) 9.8 Hz, -CH2CH2CN), 52.7 (s, OCH3),
52.8 (s, OCH3), 118.2 (d, 3J (P,C) ) 13.9 Hz, -CN), 126.1 (d,
1J (P,C) ) 100.7 Hz, ipso-Ph), 128.7 (d, 3J (P,C) ) 12.6 Hz, meta-
4
2
Ph), 132.9 (d, J (P,C) ) 2.9 Hz, para-Ph), 133.2 (d, J (P,C) )
10.1 Hz, ortho-Ph), 148.4 (d, 1J (P,C) ) 5.8 Hz, PCC), 150.8 (d,
2J (P,C) ) 25.8 Hz, PCC), 161.5 (d, 2J (P,C) ) 12.2 Hz, CO2-
CH3), 164.7 (d, 3J (P,C) ) 16.1 Hz, CO2CH3), 169.2 (s, PNC),
195.4 (d, 2J (P,C) ) 7.5 Hz, cis-CO), 198.9 (d, 2J (P,C) ) 23.3
Hz, trans-CO); 31P{1H} NMR (CDCl3) δ 21.3 (s, PPh3), 79.6 (s,
1J (W,P) ) 255.1 Hz); UV/vis (CH3CN) λ (lg ꢀ) ) 230 (4.99),
248 (4.63), 260 (4.44), 270 (4.18), 280 (3.98), 324 (3.90), 346
(3.87), 376 (3.63), 406 (3.36); IR (KBr) ν˜ 2075 (vs, CO), 1983
(vs, CO), 1945 (s, CO), 1921 (s, CO), 1907 (s, CO), 1742 (vs,
F igu r e 3. Molecular structure of 11c in the crystal
(ellipsoids represent 50% probability levels; hydrogen
atoms are omitted for clarity). Selected bond lengths [Å]
and angles [deg]: N2-C9 1.343(2), N1-P1-C7 94.26(8),
N1-P1-C6 105.15(9), C6-P1-C7 104.62(9), C9-N1-P1
110.41(13), C8-C7-P1 107.37(13), C7-C8-C9 112.40(17),
N1-C9-C8 115.30(16).
CO2), 1717 (vs, CO2) cm-1; MS (EI, 184W); m/z 853 (6) [M]+•
,
internal standard; shifts are given relative to external tet-
ramethylsilane (1H, 13C) and 85% H3PO4 (31P); only coupling
constant magnitudes are given. Electron impact (EI) (70 eV)
chemical ionization (CI) (ammonia or methane) and fast atom
bombardement (FAB) (Xenon) mass spectra were recorded on
a Finnigan MAT-8430 double-focusing mass spectrometer.
Infrared spectra were recorded on a Biorad FT-IR 165 (selected
797 (32) [M - 2CO]+, 713 (90) [M - 5CO]+, 262 (58) [PPh3],
183 (100) [PPh2]+, 73 (46) [Si(CH3)3]; MS (pos.-CI(NH3), 35Cl,
184W); m/z 958 (39) [M + H]+, 635 (74) [M + H - W(CO)5]+,
263 (100) [PPh3 + H]+. Anal. Calcd. for C33H25N3O9P2W: C,
46.45; H, 2.95; N, 4.92. Found: C, 47.69; H, 3.26; N, 4.96.
{[3,4-Bis(m eth oxycar bon yl)-2-(2-eth oxycar bon yleth yl)-
5-(N-tr iph en ylp h osp h on ioim in oyl)-2H-1,2-a za p h osp h ole-
KP ]p en ta ca r bon yltu n gsten (0)} (11b). Yield: 782 mg (87%);
mp 113 °C (dec); 1H NMR (CDCl3) δ 1.16 (t, 3J (H,H) ) 7.1 Hz,
3H, CO2CH2CH3), 1.70 (mc, 2H, PCH2CH2CO2Et), 2.22 (mc, 2H,
PCH2CH2CO2Et), 3.35 (s, 3H, OCH3), 3.92 (s, 3H, OCH3), 3.98
(mc, 2H, CO2CH2CH3), 7.38 (mc, 7H, Ph), 7.48 (mc, 3H, Ph),
7.70 (mc, 5H, Ph); 13C{1H} NMR (CDCl3) δ 14.1 (s, CH2CH3),
data given). Ultraviolett/vis spectra were recorded on
a
Hewlett-Packard HP 8452. Melting points were obtained on a
Bu¨chi 535 capillary apparatus. Elemental analyses were
performed using a Carlo Erba analytical gaschromatograph.
The κP-notation in the nomenclature is intended to differenti-
ate between P- and N-coordination of the appropriate hetero-
cycle to the metal.
Gen er a l P r oced u r e for th e P r ep a r a tion of Com p lexes
11a -d . To a solution of 7-phosphanorbornadiene complexes
3a -d (1 mmol each), dissolved in o-xylene (6 mL), carbonitrile
4b (1 mmol) and DMAD 5 (1 mmol) were added and the
2
1
27.8 (d, J (P,C) ) 4.3 Hz, PCH2CH2CO2Et), 30.0 (d, J (P,C) )
23.3 Hz, PCH2CH2CO2Et), 52.5 (s, OCH3), 52.6 (s, OCH3), 60.6
(s, OCH2CH3), 126.5 (d, 1J (P,C) ) 100.7 Hz, ipso-Ph), 128.6
(d, 3J (P,C) ) 12.6 Hz, meta-Ph), 132.6 (d, 4J (P,C) ) 2.8 Hz,
para-Ph), 133.2 (d, 2J (P,C) ) 10.1 Hz, ortho-Ph), 149.5 (s, PCC),