W. Malisch, K. Thirase, F.-J. Rehmann, J. Reising, N. Gunzelmann
FULL PAPER
NMH4C5), 1.30 [t, 2J(HCCH) ϭ 7.2 Hz, 6 H, OCH2CH3],
1.15Ϫ1.10 (m, 2 H, 8/8Ј-H, NMH4C5), 1.10Ϫ0.94 (m, 2 H, 9/9Ј-H,
NMH4C5), 0.97 [d, 3J(HCCH) ϭ 6.0 Hz, 3 H, 13-H, NMH4C5],
3.7 Hz, (CH3)3C], 13.6 (s, CH3). Ϫ 31P{1H} NMR ([D3]acetonitrile,
162.0 MHz): δ ϭ 166.8 (s). Ϫ 19F NMR ([D3]acetonitrile, 376.5
MHz): δ ϭ Ϫ148.5. Ϫ IR (acetonitrile): ν(CO) ϭ 2058 (s), 2019
(s); ν(CϭO) ϭ 1732 (m) cmϪ1. Ϫ C19H28BF4FeN4O6P (582.08):
0.96 [d, 3J(HCCH) ϭ 6.4 Hz, 3 H, 13-H, NMH4C5), 0.93 [d,
3
3J(HCCH) ϭ 6.4 Hz, 3 H, 15-H, NMH4C5], 0.92 [d, J(HCCH) ϭ calcd. C 39.21, H 4.85, N 9.63; found C 39.41, H 4.93, N 9.78.
3
6.4 Hz, 3 H, 15-H, NMH4C5], 0.82 [d, J(HCCH) ϭ 6.8 Hz, 3 H,
9)
Dicarbonyl( η5-cyclopentadienyl) {bis[ ( E) -ethoxycarbonyl-
14-H, NMH4C5], 0.81 [d, 3J(HCCH) ϭ 6.4 Hz, 3 H, 14-H,
NMH4C5]. Ϫ 13C{1H} NMR (100.6 MHz, [D3]acetonitrile): δ ϭ
methylenehydrazino] ( phenyl) phosphane}iron( II) Tetrafluoroborate
(6b): Prepared as described for 5a from 200 mg (0.53 mmol) of
{Cp(OC)2[H2(Ph)P]Fe}BF4 (4b) and 114 mg (1.00 mmol) of
N2C(H)CO2Et (2) in 10 ml of acetonitrile. Ϫ Yield 220 mg (75%).
Ϫ Light yellow microcrystalline powder. Ϫ M.p. 176°C (dec.). Ϫ
1H NMR ([D3]acetonitrile, 400.1 MHz): δ ϭ 8.86 (s, 2 H, HN),
7.73Ϫ7.37 (m, 5 H, H5C6), 7.02 [d, 4J(PNNCH) ϭ 1.2 Hz, 2 H,
HC], 5.27 [d, 3J(PFeCH) ϭ 1.5 Hz, 5 H, H5C5], 4.21 [q,
3J(HCCH) ϭ 7.2 Hz, 4 H, H2C], 1.27 [t, 3J(HCCH) ϭ 7.2 Hz, 6
H, H3C]. Ϫ 13C{1H} NMR ([D3]acetonitrile, 100.6 MHz): δ ϭ
208.7 [d, 2J(PFeC) ϭ 29.2 Hz, CO], 163.4 (s, CO2), 137.3 [d,
2
2
210.32 [d, J(CFeP) ϭ 26.16 Hz, CO], 209.44 [d, J(CFeP) ϭ 22.14
Hz, CO], 209.38 [d, 2J(CFeP) ϭ 23.14 Hz, CO], 163.28 (s, CO2),
144.24 [s, C-4, C6H2(CH3)3], 135.96 [s, CHC(O)OEt], 135.81 [s,
CHC(O)OEt], 135.88 [m, C-2, C-6, C6H2(CH3)3], 131.77 [m, C-3,
C-5, C6H2(CH3)3], 124.22 [d, 1J(CP)
ϭ 58.36 Hz, C-1,
C6H2(CH3)3], 124.13 [d, 1J(CP) ϭ 59.36 Hz, C-1, C6H2(CH3)3],
114.00 (s, C-1, C5H4), 113.78 (s, C-1, C5H4), 91.84 (s, C-2, C-3, C-
4, C-5, C5H4), 91.30 (s, C-2, C-3, C-4, C-5, C5H4), 91.06 (s, C-2,
C-3, C-4, C-5, C5H4), 90.99 (s, C-2, C-3, C-4, C-5, C5H4), 88.77 (s,
C-2, C-3, C-4, C-5, C5H4), 88.72 (s, C-2, C-3, C-4, C-5, C5H4),
85.47 (s, C-2, C-3, C-4, C-5, C5H4), 84.55 (s, C-2, C-3, C-4, C-5,
C5H4), 61.79 (s, OCH2CH3), 48.55 (s, C-7, NMC5H4), 48.43 (s, C-
7, NMC5H4), 43.73 (s, C-11, NMC5H4), 43.43 (s, C-11, NMC5H4),
35.94 (s, C-6, NMC5H4), 35.84 (s, C-6, NMC5H4), 35.39 (s, C-9,
NMC5H4), 30.07 (s, C-10, NMC5H4), 29.96 (s, C-10, NMC5H4),
28.35 (s, C-12, NMC5H4), 24.64 (s, C-8, NMC5H4), 22.35 (s, C-15,
NMC5H4), 22.29 (s, C-15, NMC5H4), 21.93 (s, C-13, NMC5H4),
21.91 (s, C-13, NMC5H4), 21.76 (s, 2-CH3, 6-CH3, (CH3)3C6H2),
21.71 [s, 2-CH3, 6-CH3, (CH3)3C6H2], 21.67 [s, 2-CH3, 6-CH3,
(CH3)3C6H2], 21.62 [s, 2-CH3, 6-CH3, (CH3)3C6H2], 20.94 [s, 4-
CH3, (CH3)3C6H2], 20.62 (s, C-14, NMC5H4), 20.59 (s, C-14,
NMC5H4), 14.24 (s, OCH2CH3), 14.23 (s, OCH2CH3). Ϫ 31P{1H}
NMR (162.0 MHz, [D3]acetonitrile): δ ϭ 65.48 (s), 65.03 (s). Ϫ 19F
NMR (376.5 MHz, [D3]acetonitrile): δ ϭ Ϫ151.4. Ϫ IR (aceto-
nitrile): ν(CO) ϭ 2049 (s), 2008 (s) cmϪ1. Ϫ C30H42BF4FeN2O4P
(668.30): calcd. C 53.92, H 6.33, N 4.19; found C 54.34, H 6.17,
N 4.09.
4
3J(PNNC) ϭ 17.1 Hz, CϭN], 134.1 [d, J(PCCCC) ϭ 1.7 Hz, C-
1
2
4], 133.1 [d, J(PC) ϭ 82.5 Hz, C-1], 131.6 [d, J(PCC) ϭ 11.1 Hz,
3
C-2/6], 130.5 [d, J(PCCC) ϭ 12.1 Hz, C-3/5], 89.1 (s, C5H5), 62.0
(s, CH2), 14.3 (s, CH3). Ϫ 31P{1H} NMR ([D3]acetonitrile, 162.0
MHz): δ ϭ 132.3 (s). Ϫ 19F NMR ([D3]acetonitrile, 376.5 MHz):
δ ϭ Ϫ151.1. Ϫ IR (acetonitrile): ν(CO) ϭ 2059 (s), 2018 (s); ν(Cϭ
O) ϭ 1738 (m) cmϪ1. Ϫ C21H24BF4FeN4O6P (602.05): calcd. C
42.03, H 3.70, N 9.34; found C 41.85, H 3.90, N 9.11.
10)
Dicarbonyl( η5-cyclopentadienyl) {bis[ ( E) -ethoxycarbonyl-
methylenehydrazino] ( 2,4,6-trimethylphenyl) phosphane}iron( II)
Tetrafluoroborate (6c): Prepared as described for 5a from 200 mg
(0.48 mmol) of {Cp(OC)2[H2(Mes)P]Fe}BF4 (4c) and 112 mg (0.98
mmol) of N2C(H)CO2Et (2) in 10 ml of acetonitrile. Ϫ Yield 218
mg (69%). Ϫ Yellow microcrystalline powder. Ϫ M.p. 184°C (dec.).
1
Ϫ H NMR ([D3]acetonitrile, 400.1 MHz): δ ϭ 8.72 (s, 2 H, HN),
7.16 (s, 2 H, HC), 6.88 [d, 4J(PNNCH) ϭ 4.0 Hz, 2 H, meta-H],
3
5.17 (s, 5 H, H5C5), 4.03 [q, J(HCCH) ϭ 6.8 Hz, 4 H, H2C], 2.26
4
[d, J(PCCCH) ϭ 1.0 Hz, 6 H, 2-H3C], 2.13 (s, 3 H, 4-H3C), 1.09
Figure 3. Atom labeling in the neomenthylcyclopentadienyl ligand
[t, 3J(HCCH) ϭ 6.8 Hz, 6 H, H3C]. Ϫ 13C{1H} NMR ([D3]acetoni-
trile, 100.6 MHz): δ ϭ 202.3 [d, 2J(PFeC) ϭ 36.2 Hz, CO], 156.2
(s, CO2), 137.3 [d, 4J(PCCCC)
ϭ
3.0 Hz, C-4], 135.1 [d,
3J(PNNC) ϭ 20.0 Hz, CϭN], 128.8 [d, 2J(PCC) ϭ 17.1 Hz, C-2/
3
1
6], 126.3 [d, J(PCCC) ϭ 10.1 Hz, C-3/5], 120.5 [d, J(PC) ϭ 66.4
Hz, C-1], 82.2 (s, C5H5), 54.9 (s, CH2), 17.4 [d, 3J(PCCC) ϭ 3.9
Hz, 2-CH3], 13.9 (s, 4-CH3), 7.4 (s, CH3). Ϫ 31P{1H} NMR ([D3]-
acetonitrile, 162.0 MHz): δ ϭ 139.14 (s). Ϫ 19F NMR ([D3]aceto-
nitrile, 376.5 MHz): δ ϭ Ϫ149.0. Ϫ IR (acetonitrile): ν(CO) ϭ 2056
(s), 2013 (s); ν(CϭO) ϭ 1730 (m) cmϪ1. Ϫ C24H30BF4FeN4O6P
(644.15): calcd. C 44.75, H 4.69, N 8.70; found C 44.57, H 4.71,
N 8.53.
11)
Dicarbonyl{bis[ ( E) -ethoxycarbonylmethylenehydrazino] -
( phenyl) phosphane}[ η5-( c-2-isopropyl-t-5-methylcyclohexan-r-1-yl) -
8)
{( tert-Butyl) bis[ ( E) -ethoxycarbonylmethylenehydrazino] - cyclopentadienyl] iron( II) } Tetrafluoroborate (6d): Prepared as de-
phosphane}dicarbonyl(η5-cyclopentadienyl) iron( II)} Tetrafluorobor- scribed for 5a from 200 mg (0.36 mmol) of {NMC5H4(OC)2-
ate (6a): Prepared as described for 5a from 200 mg (0.57 mmol) [H2(Ph)P]Fe}BF4 (4e) and 117 mg (1.03 mmol) of N2C(H)CO2Et
of {Cp(OC)2[H2(tBu)P]Fe}BF4 (4a) and 112 mg (0.98 mmol) of
N2C(H)CO2Et (2) in 10 ml of acetonitrile. Ϫ Yield 212 mg (77%).
(2) in 10 ml of acetonitrile. Ϫ Yield 246 mg (81%). Ϫ Yellow mic-
rocrystalline powder. Ϫ M.p. 179°C (dec.). Ϫ H NMR ([D3]ace-
tonitrile, 400.1 MHz): δ ϭ 8.98 (s, 2 H, HN), 7.78Ϫ7.61 (m, 5 H,
1
Ϫ Beige microcrystalline powder. Ϫ M.p. 145°C (dec.). Ϫ 1H NMR
2
([D3]acetonitrile, 400.1 MHz): δ ϭ 8.51 [d, J(PNH) ϭ 13.2 Hz, 2 H5C6), 7.40 (s, 2 H, HC), 5.58 (s, 1 H, H4C5), 5.30 (s, 1 H, H4C5),
3
H, HN], 7.32 (s, 2 H, HC), 5.44 (s, 5 H, H5C5), 4.21Ϫ4.09 (m, 4
H, H2C), 1.31 [d, 3J(PCCH) ϭ 16.8 Hz, 9 H, (H3C)3C], 1.27 [t,
3J(HCCH) ϭ 6.8 Hz, 6 H, H3C]. Ϫ 13C{1H} NMR ([D3]acetoni-
5.07 (s, 1 H, H4C5), 4.93 (s, 1 H, H4C5), 4.22 [q, J(HCCH) ϭ 7.2
Hz, 2 H, H2CϪO], 4.14 [q, 3J(HCCH) ϭ 7.2 Hz, 2 H, H2CϪO],
2.63 (s, 1 H, 6-H, NMH4C5], 1.87 (s, 1 H , 12-H, NMH4C5), 1.81
trile, 100.6 MHz): δ ϭ 208.9 [d, 2J(PFeC) ϭ 27.1 Hz, CO], 166.0 (m, 2 H, 9/9Ј-H, NMH4C5), 1.73 (m, 2 H, 11/11Ј-H, NMH4C5),
(s, CO2), 135.3 [d, 3J(PNNC) ϭ 16.1 Hz, CϭN], 85.6 (s, C5H5),
1.63 (m, 2 H, 8/8Ј-H, NMH4C5), 1.32 (s, 1 H, 7-H, NMH4C5), 1.27
1
2
3
3
62.5 (s, CH2), 40.9 [d, J(PC) ϭ 39.9 Hz, CP], 25.7 [d, J(PCC) ϭ
[t, J(HCCH) ϭ 7.2 Hz, 6 H, H3C], 0.86 [d, J(HCCH) ϭ 6.0 Hz,
1594
Eur. J. Inorg. Chem. 1998, 1589Ϫ1595