=
NH), 5.41 (br, 4H, –CH ), 5.17 (m, 2H, OCH2), 4.70 (m, 1H, CH),
3.72 (s, 3H, OCH3), 2.98–2.90 (m, 2H, PCH2), 2.26 (m, –CH2–),
benzene, 160 mg ZAlaSerphos (3d) (0.31 mmol) in 10 mL benzene
were added dropwise. The reaction mixture was strirred for 1 h at
room temp. and then all volatiles were evaporated. The residue
2.02 (m, –CH2–). 13C NMR (CD3CN): d 171.9 (s, COOCH3),
◦
1
1
155.8 (s, CONH), 136.8 (s, Cipso), 134.5 (d, JPC = 12.1 Hz, Cipso
)
was recrystallized from EtOH: yield: >95%; mp 108–110 C. H
4
3
132.1 (d, JPC = 9.6 Hz, Cortho), 130.8 (s, Cortho), 130.1 (s, Cmeta),
NMR (CD2Cl2): d 8.46/8.16 (d, J = 6.7/6.8 Hz, 1H, NHSer),
3
128.4 (s, Cpara), 128.6 (s, Cpara), 127.9 (d, JPC = 6.5 Hz, Cmeta),
8.06/7.90 (m, 2H, Haryl), 7.55–7.33 (m, 13H, Haryl), 5.75/5.50 (br,
=
=
71.2 (br, CH CH), 66.4 (s, CH2O), 52.1 (s, CH3), 51.6 (s, CH),
NHAla), 5.57/5.31 (br, 4H, –CH ), 5.17/5.13 (s, 2H, OCH2Ph),
1
3
3
32.0 (br, CH2 (cod)), 28.3 (d, JPC = 26.2 Hz, PCH2). 31P NMR
4.84/4.70 (dddd, Ja,b = 2.8/3.0 Hz, Ja,b = 13.0/12.0 Hz,
ꢀ
(CD3CN): d 20.6 (d, 1JRhP = 151.7 Hz). IR (KBr pellet) [m/cm−1]:
3Ja,NH = 6.7/6.8 Hz, Ja,P = —/8.8 Hz, 1H, CHSer), 4.60/4.09
3
(m, 1H, CHAla), 3.72/3.69 (s, 3H, OCH3), 3.27/3.01 (ddd, 2Jb,P
=
=
3307 (s, NH str.), 2915, 2877 (s, CH str.), 1741 (s, C O), 1707
6.6/3.8 Hz, 3Ja,b = 12.0/13.0 Hz, 2Jb,b = 14.7 Hz/—, 1H, CH2P),
=
ꢀ
(ss, (C O) amide I), 1507 (ss, (N–H) amide II), 1430 (m), 1381,
2
3
ꢀ
ꢀ
1354, 1260, 1212, (ss), 1041 (s), 1028, 797, 757, 699. UV/VIS (thf)
kmax/nm (e/l mol−1 cm−1): 402.2 (2174), 279.1 (5042). Anal. Calc.
for C32H36ClNO4PRh (667.96 g mol−1): C: 57.54%, H: 5.43%, N:
2.09%, P: 4.64. Found: C: 57.3%, H: 5.4%, N: 2.3%, P: 4.6%.
2.87/2.85 01 (ddd, Jb ,P = 12.2/14.2 Hz, Ja,b = 3.0/2.8 Hz,
2
ꢀ
Jb,b = 14.7 Hz/—, 1H, CH2P), 2.45/2.09 (br, 4H, –CH2– (cod)),
2.34/1.90 (br, 4H, –CH2– (cod)), 1.49/1.44 (d, 3JH,H = 7.0/7.0 Hz,
CH3Ala). 13C NMR (CD2Cl2): d 173.0/172.5 (s, COOCH3),
171.9/171.7 (s, CONH), 156.1/155.9 (s, CONH), 137.3/137.3 (s,
4
Chloro(g -1,5-cyclooctadiene)[R(S)-3-diphenylphosphanyl-
1
Cipso), 135.4/134.8 (d, JP,C = 12.3/12.3 Hz, Cipso), 133.1/132.6
methyl-N-(tert-butoxycarbonyl)serinate]rhodium(I) [RhCl-
(d, 2JP,C = 9.9/9.9 Hz, Cortho), 128.6/128.2 (d, 3JP,C = 7.0/7.0 Hz,
Cmeta), 131.5/131.1 (s, Cortho), 130.7/130.7 (s, Cmeta), 128.9/128.8
(s, Cpara), 128.7/128.7 (s, Cpara),73.3/72.2/71.5 (d, J = 13.5 Hz,
CH (cod)), 66.9/66.9 (s, CH2Ph), 58.5/58.5 (s, OCH3), 51.0/51.0
(s, CHAla), 50.7/50.4 (s, CHSer), 33.5/33.2/32.7 (br, CH2 (cod)),
29.1/28.7 (d, 1JC,P = 23.2/23.2 Hz, CH2P), 20.1/19.7 (s, CH3(Ala)).
31P NMR (CD2Cl2) d 20.3/18.4 (d, 1JP,Rh = 150.7/150.7 Hz). 103Rh
NMR (CD2Cl2) d 372/365. IR (KBr pellet) [m/cm−1]: 3258 (s, NH
(
BocSerphos)(cod)] (9). Yield: 62%; mp 105 ◦C. 1H NMR
(CDCl3): d 7.88 (m, 2H, Haryl), 7.53–7.26 (m, 8H, Haryl), 6.82
3
=
(d, 1H, J = 7.14 Hz, NH), 5.54 (br, 2H, –CH ), 4.72 (m, 1H,
=
CH), 4.24 (br, 2H, CH ), 3.73 (s, 3H, OCH3), 3.18–3.03 (m, 2H,
PCH2), 2.43 (m, –CH2–), 2.04 (m, –CH2–), 1.52 (s, 9H, C(CH3)3).
13C NMR (CDCl3): d 172.1 (d, 3JPC = 13.1 Hz, COOCH3), 155.5
1
4
(s, CONH), 134.5 (d, JPC = 11.8 Hz, Cipso) 132.1 (d, JPC
=
9.7 Hz, Cortho), 129.6 (s, Cpara), 128.2 (d, 3JPC = 8.2 Hz, Cmeta), 104.5
1
2
=
=
str.), 1735 (ss, C O), 1717 [ss, (C O) amide I], 1509 [ss, (N–H)
amide II]. Anal. Calc. for C35H41ClN2O5PRh (739.05 g mol−1): C:
56.88%, H: 5.59%, N: 3.79%. Found: C: 56.90%, H: 5.61%, N:
3.78%.
=
(m, CH ), 78.4 (s, C(CH3)3), 70.5 (dd, JRhC = 53.7 Hz, JCP
=
=
13.7 Hz, CH CH), 66.4 (s, CH2O), 52.2 (s, CH3), 51.1 (s, CH),
1
32.9, 32.2, 30.5 (s, CH2 (cod)), 29.1 (d, JPC = 26.1 Hz, PCH2),
28.6 (s, CH2 (cod)), 28.14 (s, C(CH3)3). -31P NMR (CDCl3): d
20.8 (d, 1JRhP = 150.0 Hz). IR (KBr pellet) [m/cm−1]: 3296 (s, NH
Synthesis of (g4-1,5-cyclooctadiene)[R(S)-3-diphenylphosphane-
methyl-N -(carbobenzyloxy)serinate)rhodium(I) hexafluorophos-
phate [Rh(cod)(j2 -ZSerphos)]PF6 (12). 0.31 g [RhCl(cod)-
(ZSerphos)] 10 (0.46 mmol) was dissolved in 30 mL benzene. To
this yellow solution, 148 mg [Ag(MeCN)2]PF6 (0.46 mmol) was
added under exclusion of light. After 1 h stirring at room temp.,
the formed precipitate (AgCl) was filtered off and the filtrate was
slowly concentrated to dryness dried under vacuum to give a
=
=
str.), 2962–2830 (s, CH str.), 1754 (ss, C O), 1697 [ss, (C O)
amide I], 1504 [ss, N–H amide II], 1431 (m, P–C str.), 1362, 1258
(m, P–CH2), 1214, (m), 1160 (s, C–O), 1096 (s), 1017, 801 (s,
monosub. arene), 744 (s, monosub. arene), 691. UV/VIS (thf)
kmax/nm (e/l mol−1 cm−1): 400.1 (1681), 287.1 (5500). Anal. Calc.
for C29H38ClNO4PRh (633.95 g mol−1): C: 54.94%, H: 6.04%, N:
2.21%. Found: C: 54.3%, H: 5.97%, N: 2.3%.
4
◦
1
Chloro(g -1,5-cyclooctadiene)[R(S)-3-diphenylarsanylmethyl-
yellow solid. Yield: 97%; mp 74 C. H NMR (CDCl3): d 7.93–
7.34 (m, 15H, Haryl), 6.26 (d, 1H, 3J = 8.2 Hz, NH), 5.37 (br, 2H,
N-(carbobenzyloxy)serinate]rhodium(I) [RhCl(ZSerars)(cod)]
(11). Yield: 35.5%; mp 126 ◦C. 1H NMR (CD3CN): d 7.70–7.66
(m, 2H, Haryl), 7.49–7.2 (m, 13H, Haryl), 6.98 (d, 1H, 3J = 7.62 Hz,
NH), 5.11 (dd, 2H, 2J = 16.3 Hz, OCH2), 4.59 (m, 1H, CH), 4.27
=
–CH ), 5.01 (m, 2H, OCH2), 4.84 (m, 1H, CH), 4.33 (br, 2H,
=
–CH ), 3.85 (s, 3H, OCH3), 3.23–2.80 (m, 2H, PCH2), 2.47 (m, –
CH2–), 2.08 (m, –CH2–). 13C NMR (CDCl3): d 171.9 (s, COOCH3),
158.5 (s, CONH), 136.3 (d, 1JPC = 10.1 Hz, Cipso), 134.5 (s, Cipso),
=
(s, 4H, –CH ), 3.68 (s, 3H, OCH3), 2.89–2.77 (m, 2H, AsCH2),
2.7 (m, –CH2–), 1.86–1.79 (m, –CH2–). 13C NMR (CD3CN): d
172.4 (s, COOCH3), 156.2 (s, CONH), 137.4 (s, Cipso), 134.3 (s,
Cipso) 130.6 (s, Cortho), 130.35 (s, Cpara), 129.4 (s, Cmeta), 128.9 (s,
4
133.7 (d, JPC = 12.4 Hz, Cortho), 131.8 (s, Cortho), 131.7 (s, Cmeta),
130.98 (s, Cpara), 129.1 (s, Cpara), 128.8 (d, 3JPC = 6.8 Hz, Cmeta), 108.5
=
=
(m, CH CH), 71.3 (br, CH CH), 68.3 (s, CH2O), 53.9 (s, CH3),
52.55 (s, CH), 31.9 (br, CH2 (cod)), 27.5 (d, 1JPC = 26.8 Hz, PCH2).
31P NMR (CDCl3): d 25.7 (d, 1JPRh = 148.5 Hz, RhPCH2), −143.0
=
Cortho), 128.5 (s, Cpara), 128.3 (s, Cmeta), 82.2 (br, CH CH), 66.8 (s,
CH2O), 52.6 (s, CH3), 52.1 (s, CH), 31.0 (s, CH2 (cod)), 28.0 (s,
AsCH2). IR (KBr pellet) [m/cm−1]: 3272 (s, NH str.), 2911, 2872
(sept, JPF = 713 Hz, PF6−). IR (KBr pellet) [m/cm−1]: 3384 (br,
1
=
=
(s, CH str.), 1743 (ss, C O), 1710 (s, amide I, C O), 1527 (s,
amide II), 1431 (m), 1211 (ss), 1044, 1025, 734, 693. UV/VIS (thf)
kmax/nm (e/l mol−1 cm−1): 374.8 (1242), 277.1 (5000). Anal. Calc.
for C32H36AsClNO4Rh (711.91 g mol−1): C: 53.99%, H: 5.10%, N:
1.97%. Found: C: 47.5%, H: 5.14%, N: 1.3%.
=
NH str.), 2918, 2876 (s, CH str.), 1725 (s, C O), 1623 (ss, amide
I), 1432 (m), 1382, 1259, 1218, 1096 (s), 1026, 839 (ss, PF str.), 695.
Anal. Calc. for C29H38F6NO4P2Rh (777.48): C: 49.43%, H: 4.67%,
N: 1.8%. Found: C: 50.4%, H: 4.9%, N: 2.0%.
Synthesis of (g4-1,5-cyclooctadiene)-[2-R(S)-2ꢀ-S(R)-(benzyloxy-
carbonylamino)propionylamino)-3-(diphenylphosphanyl)methylpro-
pionate]rhodium(I) hexafluorophosphate [Rh(cod)(j2-ZAlaSerphos)]-
PF6 (13). 42 mg [RhCl(cod)(ZAlaSerphos)] 10 (0.06 mmol)
were dissolved in 5 mL benzene and 23 mg TlPF6 (1.1 eq.)
Synthesis of chloro(g4 -1,5-cyclooctadiene)[2-R(S)-2ꢀ -S(R)-
(benzyloxycarbonylamino)propionylamino)-3-(diphenylphosphanyl)-
methylpropionate]rhodium(I) [RhCl(cod)(ZAlaSerphos)] (10). To
a solution of 80 mg [Rh2(l-Cl)2(cod)2] (0.15 mmol) in 10 mL
1 4 6 | Dalton Trans., 2006, 137–148
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