L,3-Bis(trimethylsilyl)-l,3,2-diazaphospha-[3]ferrocenophanes

Article abstract of DOI:10.1002/zaac.200900494

The 2-ferf-butyl, 2-phenoxy, and 2-diethylamino derivatives of l,3-bis(trimethylsilyl)-l,3,2-diazaphospha-[3]ferrocenophane were prepared, and the molecular structure of the latter was determined by Xray diffraction. The phosphines could be oxidized by their slow reactions with, sulfur or selenium, and the molecular structures of three Sulfides and one selenide were determined. In contrast, the synthesis of oxides was less straightforward. All new compounds were characterized, in solution by multinuclear magnetic resonance methods (ID and 2D ¹H, ¹³C, ¹⁵N, ²⁹Si, ³¹P, and ⁷⁷Se NMR spectroscopy).

Full text of DOI:10.1002/zaac.200900494

ARTICLE
DOI: 10.1002/zaac.200900494
1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophanes
Bernd Wrackmeyer,*[a] Elena V. Klimkina,[a] and Wolfgang Milius[a]
Dedicated to Professor Yuri N. Bubnov on the Occasion of His 75th Birthday
Keywords: Ferrocenes; Ferrocenophanes; Aminophosphines; NMR spectroscopy; X-ray diffraction
Abstract. The 2-tert-butyl, 2-phenoxy, and 2-diethylamino derivatives sulfides and one selenide were determined. In contrast, the synthesis
of 1,3-bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophane were pre- of oxides was less straightforward. All new compounds were charac-
pared, and the molecular structure of the latter was determined by X- terized in solution by multinuclear magnetic resonance methods (1D
1
ray diffraction. The phosphines could be oxidized by their slow reac- and 2D H, 13C, 15N, 29Si, 31P, and 77Se NMR spectroscopy).
tions with sulfur or selenium, and the molecular structures of three
Introduction
Aminophosphines, which are well known for many years [1–
3], are attracting increasing interest as ligands for transition
metal complexes [3, 4]. In this context, bulky substituents at
nitrogen creating at least in part a rigid backbone may be use-
ful, in order to stabilize a lower coordination number of the
metal atom as a prerequisite of catalytic activity. At the same
time, it might be an advantage to reduce the basicity of the
nitrogen atoms. For these purposes, 1,1'-bis(trimethylsilylam-
ino)ferrocene (2) [5], readily prepared from 1,1'-diaminoferro-
cene (1) [6, 7] should be a suitable starting material to accom-
modate the phosphorus atom between the two nitrogen atoms
and form the 1,3,2-diazaphospha-[3]ferrocenophane unit. Re-
cently, we have reported that this works fairly well without
N-trimethylsilyl groups [8, 9] (Scheme 1, compounds 3–5). In-
deed, the N-trimethylsilyl and other N-silyl derivatives have
already proved useful in the synthesis of numerous 1,3-diaza-
2-element-[3]ferrocenophanes, in which either a main group
element [5, 10–16] or a transition metal [17–22] takes the place
between the nitrogen atoms.
Although numerous N-silylaminophosphines were prepared
Scheme 1. 1,1'-Diaminoferrocenes 1, 2 and known 1,3,2-diazaphos-
[1–4, 23–26], cyclic derivatives were surprisingly rare [27],
pha-[3]ferrocenophanes 3–5.
and only few were structurally characterized [28]. There are
also rather few 29Si NMR spectroscopic data reported, in spite
of the structurally diagnostic value of the geminal coupling
phosphorus atom and the N–Si bond vector [29, 30]. Some
2
constant J(31PN29Si), which indicates by its sign and magni-
of the N-trimethylsilylaminophosphines have proved useful as
tude the mutual orientation of the lone pair of electrons at the
starting material for valuable and unusual phosphorus/nitrogen
compounds, e.g. the amino-iminophosphines [31]. Herein, we
* Prof. Dr. B. Wrackmeyer
report on the synthesis, characterization, and some properties
of 1,3-bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophanes.
Fax: +49-921-552157
E-Mail: b.wrack@uni-bayreuth.de
[a] Laboratorium für Anorganische Chemie
Universität Bayreuth
Results and Discussion
The two most convenient routes to the title compounds ap-
pear to be salt metathesis reactions, starting from 2 via the
95440 Bayreuth, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.200900494 or from the
author.
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Z. Anorg. Allg. Chem. 2010, 636, 784–794

1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]erferrocenophanes
Table 1. 13C, 31P, 29Si, 15N, and 77Se NMR spectroscopic dataa) of the 1,3-bis(trimethylsilyl)-2-R-1,3,2-diazaphospha-[3]ferrocenophanes 8–10.
8ab)
8cb)
8d
9ab)
9cb)
10ad)
10cb)
10db)
P(E)R
δ31P
P–tBu
P(S)tBu
P(Se)tBu
P–OPh
P(S)OPh
P–NEt2
132.6
P(S)NEt2
P(Se)NEt2
67.6 {17.8}
<776.5>
5.6 (0.9)
[60.0]
133.4 {39.1} 106.5 {10.6} 103.9 {12.3} 139.2 {40.4} 70.1 {16.3}
<747.7>
77.2 {15.3}
δ13C(SiMe3)
δ13C(PR)
2.6 (10.0)
[57.6]
5.6 (0.8)
[59.7]
6.2 (0.7)
[59.6]
29.9 (3.3)
Me
1.8 (10.3)
[57.4]
119.9 (9.7) 121.8 (5.4)
3.9 (1.1)
[59.4]
2.16 (10.9) 4.8 (1.0)
[57.5]
11.7 (3.6)
Me
[59.5]
11.1 (6.1)
Me
30.0 (20.0) 29.7 (2.7)
10.7 (6.0)
Me
Me
Me
Co
122.2 (1.8) 124.7 (1.7)
Cp Cp
129.7 (<0.5) 129.7 (1.4)
Cm Cm
Co
35.9 (41.8) 41.5 (84.4)
P–C P–C
42.8 (71.2)
P–C
38.2 (17.8) 38.6 (3.9)
CH2 CH2
39.1 (4.4)
CH2
155.7 (9.7) 152.3 (8.2)
Ci
Ci
δ13C(fc–C1)
δ13C(fc–C2)
δ13C(fc–C3)
δ13C(fc–C4)
δ13C(fc–C5)
δ29Si
103.5 (6.6) 98.4 (8.1)
70.9 (<0.5) 71.6 (2.4)
65.1 (<0.5) 66.6 (0.5)
67.9 (<0.5) 69.5 (0.5)
66.6 (0.5)
9.8 {39.3} 12.9 {10.7}
[57.7]
–343.4
81.4
–
99.1 (10.1)
71.5 (2.1)
98.6 (2.9)
70.1 (0.5)
95.1 (9.4)
71.6 (6.2)
101.1 (4.0) 96.8 (8.4)
97.1 (10.2)
71.8 (4.2)
65.9 (0.5)
69.3 (<0.5)
65.2 (<0.5)
14.3 {17.2}
[59.7]
69.8 (0.6)
71.6 (4.7)
68.1 (<0.5)e)
69.7 (<0.5)
66.8 (<0.5)e)
14.0 “1.7”
65.3 (<0.5) 67.0e)
68.7 (<0.5) 69.6
64.6 (<0.5) 65.8 (0.8)
67.8 (<0.5) 69.0 (<0.5)
68.0 (<0.5)
68.5 (1.3)
66.6e)
66.6 (1.2)
64.9 (<0.5)
11.4 {40.3} 15.3 {16.2}c) 9.8 {37.9} 13.3 {15.3}
[59.6]
–330.1
29.0
–
{12.5} [59.7] [57.5]
[57.6]
–334.6
81.1
–327.1
37.5
[59.5]
–327.6
5.7
–318.0
2.5
δ15N (NSi)
1J(31P,15N)
δ15N (NEt2)
1J(31P,15N)
δ77Se
–332.2
35.7
–
–317.1
81.6
–
–318.1c)
4.2
–
–326.9
15.4
–317.1
7.9
–
–
–131.5 <747.1> –
–
–133.1 <776.8>
a) Measured in CD2Cl2 (8a, 8c, 8d, 9a, 9c, 10a,), [D8]toluene (10c, 10d); coupling constants J(31P,13C) ( 0.5 Hz) are given in parentheses;
n
coupling constants 2J(31P,29Si) ( 0.5 Hz) are given in braces; coupling constants 1J(29Si,13C) ( 0.5 Hz) are given in brackets; coupling constants
1J(77Se,31P) are given in < >, J(77Se,29Si) are given in “ ”. b) The assignment of the NMR signals is based on H-1H NOESY [32], and 2D H/
3
1
1
13C gHSQC [33] experiments. c) In [D8]toluene. d) δ57Fe 1098.4 (Ref. [15]). e) Assignment might be reversed.
N,N'-dilithium (6) or the magnesium derivative (7)
The routes shown in Scheme 2 seem to be straightforward.
(Scheme 2). The PIII compounds 8a, 9a, and 10a can be oxi- However, we encountered difficulties owing to slow reactions
dized in their reactions with sulfur or selenium to give the of the amides 6 or 7 and to the unexpected reactivity of the
respective sulfides and selenides. Most relevant NMR spectro- N–Si bond(s) in intermediates as well as in the final products.
scopic data are given in Table 1.
Some relevant NMR spectroscopic data of an intermediate and
Scheme 2. Synthesis of 1,3-bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophanes 8a–10a and their reactions with sulfur and selenium.
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B. Wrackmeyer, E. V. Klimkina, W. Milius
ARTICLE
Table 2. 13C, 31P, 29Si, and 77Se NMR spectroscopic dataa) of the compounds 11, 12, 14.
11
P–tBu
12
P–tBu
14
P(O)H
δ31P
160.9 (br)
111.1 {12.7} <760.6>
4.7 (0.6)
22.8 {9.2}
1J(31P,1H) = 595.1 Hz
1.6 (5.3)
δ13C(SiMe3)
δ13C(PR)
0.3 [57.0] (Me3SiNH)
3.1 (14.0) [58.2] (Me3SiNP)
25.9 (21.6) (Me)
28.7 (2.6) Me,
41.5 (75.6) PC
δ1H (PH) = 7.48
37.7 (41.5) (CP)
1J(31P,1H) = 595.1 Hz
δ13C(fc–C1,6
δ13C(fc–C2,7
δ13C(fc–C3,8
δ13C(fc–C4,9
)
101.1 (br), 109.1
101.4 (9.9), 91.5 (14.5)
71.6 (2.0), 70.8 (1.7),
69.3 (0.7), 69.2 (0.5),
69.1, 68.6 (0.9),
68.0, 64.3
90.1 (2.1)
70.5
)
)
)
58.0 (br), 58.4,
65.9, 66.0,
68.9
67.5 (br), 68.8 (5.5),
68.7 (br), 68.8 (br)
2.8 [57.2] (SiMe3)
11.8 {30.5} (Me3SiNP)
67.1
δ13C(fc–C5,10
δ29Si
)
66.1
15.5 {12.7}
14.7 {9.2}
a) Measured in CD2Cl2 (11, 12), CDCl3 (14); coupling constants J(31P,13C) ( 0.5 Hz) are given in parentheses; coupling constants J(31P,29Si)
n
2
1
1
(
0.5 Hz) are given in braces; coupling constants J(29Si,13C) ( 0.5 Hz) are given in brackets; coupling constants J(77Se,31P) are given in <
>; (br) denotes broad 13C resonances due to dynamic effects.
side products are given in Table 2, and some NMR spectro-
In the case of 10a, the oxidation with sulfur and selenium
scopic data are also given in Scheme 2. Thus, the reaction gave the expected products 10c and 10d, respectively, without
leading to 8a proceeds partially through formation of 11, which appreciable side reactions. In contrast, oxidation of 10a with
appears to be unstable in CD2Cl2 and is slowly converted into Me3Si–O–O–SiMe3 failed, and a mixture was obtained, which
the known 3a [8] (Scheme 3). Although traces of water cannot contained 10a together with a partially hydrolyzed product 13
be completely ruled out, it is likely that CD2Cl2 is also respon- and the oxidized product 14 (Scheme 5). It is conceivable that
sible.
the exocyclic P–N bond of 10a was hydrolyzed, and the P–OH
function rearranged into the P(O)H moiety in 14. However, the
oxide 10b was formed, when an unsealed solution of 10a in
CD2Cl2 was kept in the NMR tube for 60 days at room temper-
ature, which indicates a slow reaction of 10a with oxygen.
This sample also contained the compounds 13 and 14.
NMR Spectroscopy, Solution State Structures
Because of the bulkiness of the N-trimethylsilyl groups, the
1,3,2-diazaphospha-[3]ferrocenophanes studied here prefer the
exocyclic substituent at phosphorus to be located in anti-posi-
tion to the N–Si bond vectors. This is shown by the molecular
structure of 10a as well as by those of sulfides and selenides
(vide infra), since the configuration of the phosphorus atom
usually does not change upon oxidation. For the solution state
structures, the large magnitude |2J(31PN29Si)|, observed for 8a,
Scheme 3. In the reaction of 6 or 7 with tBuPCl2 the intermediate 11
can be identified when the reaction solution was taken up in CD2Cl2
and studied by NMR spectroscopy.
9a, and 10a, is a diagnostic criterion for this structural feature
1
The attempt to oxidize 8a with bis(trimethylsilyl)peroxide in the PIII compounds [29, 30]. On this basis, the H NMR
1
Me3Si–O–O–SiMe3, in hexane (60 hours at room temperature) spectroscopic signals can be assigned by H-1H NOE differ-
gave mainly 3a and its known oxide 3b [8] (ratio 85:15). In ence experiments (Figure 1), which provide help for the as-
contrast to the reaction of 8a with sulfur, the oxidation of 8a signment of the 13C NMR spectra. Although the observed NOE
1
1
with selenium proceeded more slowly, leading to a 1:1 mixture between H(SiMe3) and H(tBu) nuclei may be surprising at a
of 8a and its selenide 8d after 48 hours. When this mixture first glance, the H···H distances between these groups are not
was dissolved in CD2Cl2 and the solution kept for 5 days at too long as can be estimated from the determinations of the
room temperature, it contained 8a, 8d, and 12 in a ratio 3:12:5 solid-state structure. In the example of 8c (Figure 1) the short-
(Scheme 4) along with siloxane (Me3Si)2O. After several est distance H(SiMe3)···H(tBu) is approximately 232 pm, even
months, we still found 8d together with much of the known less than e.g. the shortest distance between H(SiMe3) and
selenide 3d instead of 12. Similarly, treatment of the phenoxy H2(fc) (≈ 288 pm).
derivative 9a with sulfur or selenium led slowly to the desired
sulfide 9c or selenide 9d.
Typical 13C NMR spectra are shown in Figure 2 for 10a and
10d and illustrate the changes in the magnitude of J(31P,13C)
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Z. Anorg. Allg. Chem. 2010, 784–794

1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]erferrocenophanes
Scheme 4. Side reactions, when 8a and 9a were treated with sulfur and selenium (9d was identified in the reaction mixture by its 31P and 29Si
NMR spectroscopic data).
Scheme 5. Attempted oxidation of 10a (10b and 13 were identified in
the reaction solution by their 31P and 29Si NMR spectroscopic data).
when PIII was transformed into PV. Figure 3 gives evidence
that 29Si NMR spectra provide useful and complementary in-
formation to the 31P NMR spectra, which are usually meas-
ured. In the case of the oxidation of 8a with selenium, the
reaction is slow. However, further products are only formed
after addition of CD2Cl2. The combined application of 1H, 31P
and 29Si NMR spectroscopy to study the attempted oxidation
of 10a reveals the nature of the somewhat unexpected product
14 (Figure 4).
Figure 1. 399.8 MHz 1H-1H NOE difference spectra (gradient en-
hanced [32]) of 8c (in CD2Cl2; at 23 °C; relaxation delay 2.0 s; mixing
time 0.8 s). (A) Normal 1H NMR spectrum. (B) Irradiation of
1H(SiMe3): NOE for 1H(CMe3) and (fc)1H2,2'. (C) Irradiation of
1H(CMe3): NOE for 1H(SiMe3) and (fc)1H5,5'. (D) Irradiation of
The 31P chemical shifts follow the established trends for PIII
and PV compounds [35], and this is also true for δ77Se and the
coupling constants 1J(77Se,31P) [36]. The δ15N(Si) values cover
a narrow range of only 27 ppm and do not mirror the influence
of the other substituents at the phosphorus atom in a diagnostic
1
1
(fc)1H5,5': NOE for H(CMe3), (fc)1H4,4' and weak for H(SiMe3).
manner. However, the coupling constants 1J[31P,15N(Si)] sign [37]. In the case of 10a, J[31P,15N(Et)] is surprisingly
clearly allow to distinguish between PIII and PV. For PIII, these small (37.5 Hz) for PIII, and it is tempting to relate this to a
constants are fairly large (≈ 81 Hz) and positive [37], whereas change in the nature of the lone pair of electrons at the nitrogen
for PV the coupling constants are small and may be of either atom, as indicated by the structural parameters (vide infra).
1
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B. Wrackmeyer, E. V. Klimkina, W. Milius
ARTICLE
Figure 2. (A) 62.9 MHz 13C{1H} NMR spectrum of 10a (in CD2Cl2, at 23 °C). (B) 62.9 MHz MHz 13C{1H} NMR spectrum of the mixture
containing 10d and 2 (in [D8]toluene, at 23 °C).
Figure 3. The reaction solution obtained from the reaction of 8a with Se. (A) 49.7 MHz 29Si{1H} NMR spectrum (refocused INEPT; 23 °C)
after 48 h at room temperature in toluene-hexane. The mixture, now dissolved in CD2Cl2, contains 8a and 8d (ratio 1:1). The 29Si satellites for
3
1J(29Si,13CMe) are marked by filled circles; the 77Se satellites for J(77Se,29Si) are marked by arrows. (B) 49.7 MHz 29Si{1H} NMR spectrum
(refocused INEPT) of the same sample after 5 days at room temperature in CD2Cl2. The mixture contains 8a, 8d, and 12 (ratio 3:12:5).
Such a change would be less important for the PV-compounds, atoms of the exocyclic NEt2 group in 10a [Σ∠(CN(3)C,
where the lone pair of electrons at phosphorus is engaged.
CN(3)P) = 339.8°], 10c [Σ∠(CN(3)C, CN(3)P) = 348.1°] and
10d [Σ∠(CN(3)C, CN(3)P) = 347.4°] are pyramidal, which is
unusual [38] for such phosphorus/nitrogen compounds. Pre-
sumably, this is enforced by the rigid ferrocenediyl backbone
in order to avoid close contacts with the N–Et groups. The
phosphorus atoms in the PV compounds are in distorted tetra-
hedral surroundings, and in 10a, the pyramidal arrangement of
the phosphorus atom is typical of PIII [Σ∠(NPN) = 309.8°].
The P–S bond lengths in 8c, 9c, and 10c are almost identical,
X-ray Structural Studies of the 1,3-Bis(trimethylsilyl)-1,3,2-
diazaphospha-[3]ferrocenophanes 8c, 9c, 10a, 10c, and 10d
The molecular structures are shown in the Figure 5 (8c), Fig-
ure 6 (9c), Figure 7 (10a), and Figure 8 (10c, 10d). In all
cases, intermolecular interactions are negligible. The surround-
ings of the nitrogen atoms are trigonal planar within the experi-
mental errors. Interestingly, the surroundings of the nitrogen showing no particular influence of the tBu, OPh or NEt2 group
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1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]erferrocenophanes
Figure 4. 1,3-Bis(trimethylsilyl)-2-hydro-1,3,2-diaza-phosphoryl-[3]ferrocenophane (14). (A) Normal 250.1 MHz 1H NMR spectrum in CD2Cl2.
(B) 250.1 MHz 1H{31P} NMR spectrum in CD2Cl2. (C) Normal 101.3 MHz 31P NMR spectrum in CDCl3. (D) 101.3 MHz 31P{1H} NMR
spectrum in CDCl3. (E) 49.7 MHz 29Si{1H} NMR (refocused INEPT) spectrum in CD2Cl2.
at phosphorus. As usual, slightly longer endocyclic P–N bond
lengths in 10a with PIII are found, when compared with those
of the PV-compounds. On the other hand, the N–Si bonds in
10a are shorter than in the PV derivatives [37]. Expectedly, the
angles at the endocyclic nitrogen atoms are somewhat more
acute in the N–SiMe3 derivatives studied here than in the N–
H derivatives with comparable configuration at phosphorus
(5a, 5b), reported previously [9]. In all cases, the positions of
the cyclopentadienyl rings do not deviate significantly from
eclipsed arrangements (Table 3, ∠τ), whereas the structural
features of the ferrocenophane ring enforce a slight tilt (Ta-
ble 3, ∠α) of the cyclopentadienyl rings out of their parallel
arrangement towards iron. The C–N bond vectors are shifted
slightly out of the C5-planes of the cyclopentadienyl rings (Ta-
ble 3, ∠β), also towards iron.
Figure 5. Molecular structure of 8c (ORTEP plot, 30 % probabilities,
hydrogen atoms are omitted for clarity; for selected distances and an-
gles see Table 3).
Figure 6. Molecular structure of 9c (ORTEP plot, 30 % probabilities, Figure 7. Molecular structure of 10a (ORTEP plot, 30 % probabilities,
hydrogen atoms are omitted for clarity; for selected distances and an- hydrogen atoms are omitted for clarity; for selected distances and an-
gles see Table 3).
gles see Table 3).
Z. Anorg. Allg. Chem. 2010, 784–794
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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789

B. Wrackmeyer, E. V. Klimkina, W. Milius
ARTICLE
Figure 8. (A) Molecular structure of 10c (ORTEP plot, 30 % probabilities, hydrogen atoms are omitted for clarity; for selected distances and
angles see Table 3). The arrangement of the second symmetrically independent molecule in 10c is similar. (B) Molecular structure of 10d
(ORTEP plot, 30 % probabilities, hydrogen atoms are omitted for clarity; for selected distances and angles see Table 3). The arrangement of
the second symmetrically independent molecule in 10d is similar.
Table 3. Selected bond lengths /pm and angles /dega) of the 1,3-bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophanes 8c, 9c, 10a, 10c, and
10d, and of the 2-phenoxy-1,3,2-diazaphospha-[3]ferrocenophane 5a [9] for comparison.
8c
9c
10ab)
10cc,d)
10dd,e)
5a
R = tBu
E = S
R = OPh
E = S
R = NEt2
R = NEt2
E = S
R = NEt2
E = Se
R = OPh
P–N(1)
168.5(2)
166.1(2)
165.6(2)
170.0(5)
170.6(6)
167.4(5)
166.5(5)
166.5(4)
167.0(4)
169.4(3)
P–N(2)
–
170.0(3)
P–R
P–E
N(1)–Si(1)
N(2)–Si(2)
N(1)···N(2)
C(1)···C(6)
Fe···P
N(1)–P–N(2)
N(1)–P–R
N(2)–P–R
N(1)–P–E
N(2)–P–E
R–P–E
187.3(5), (P–C(9))
194.91(16)
179.3(3)
162.09(18), (P–O) 172.9(8), (P–N(3))166.5(5), (P–N(3)) 167.6(4), (P–N(3))
166.1(3), (P–O)
193.11(9)
179.6(2)
178.4(2)
274.1
–
195.0(2)
179.5(5)
179.6(5)
277.1
303.4
351.4
112.2(3)
104.9(2)
104.4(2)
110.00(18)
109.71(19)
104.9(2)
116.5(4)
115.4(3)
119.7(4)
120.0(3)
123.7(3)
115.4(3)
58.6
210.36(14)
180.8(4)
180.3(4)
275.9
302.8
351.7
111.6(2)
104.3(2)
104.7(2)
110.70(14)
109.78(14)
115.55(15)
115.6(3)
–
–
175.2(6)
175.0(7)
274.0
–
–
–
278.6 [N···N(0A)]
272.3
297.0 [C(1)···C(1A)] 302.3
303.1
362.9
307.4
362.1
350.0
360.1
111.51(17)
108.57(12)
–
111.47(11)
105.81(10)
100.92(11)
111.62(8)
113.43(8)
112.89(8)
116.75(17)
117.8(5)
107.1(3)
100.9(3)
101.8(3)
–
106.68(16)
100.13(17)
94.44(16)
109.34(9)
–
–
–
–
–
–
–
109.47(15)
C(1)–N(1)–Si(1) 111.4(2)
C(6)–N(2)–Si(2) 117.27(17)
117.4(4)
115.4(4)
123.2(5)
120.4(4)
119.2(4)
124.0(3)
58.5
P–N(1)–C(1)
P–N(2)–C(6)
P–N(1)–Si(1)
P–N(2)–Si(2)
Distance of P
from the plane,
Fe–C(1)–N(1)–
N(2)–C(6) /pmf)
C5 / C5 (α)
124.4(2)
120.07(17)
122.78(14)
122.31(13)
38
119.95(18)
123.4(5)
123.29(12)
118.4(3)
120.2(3)
125.9(2)
124.2(2)
–
127.0(3)
–
61.5
58.2
55.3
13.2
11.2
0.4
10.8
0
9.8
0.2
9.8
9.2
4.5
C5 / N(1) (β1)
C5 / N(2) (β2)
2.3 (towards iron)
0.5 (towards iron)
0.5 (towards iron) 0.3 (towards iron) 0.8 (towards iron) 0.6 (bent away from 2.1 (towards iron)
iron)
C5–Fe–C5 (γ)
172.5
172.6
171.7
173.6
173.4
172.4
C5 / C5 (twist) (τ) 0 (symmetry)
0.1
0.1
0.2
0.1
0.3
Fe–C5 (center)
162.2
163.7, 163.5
163.4, 163.7
163.2, 162.6
162.3, 162.2
164.0, 164.3
a) The definition of the angles α, β, γ and τ is given in ref. [15, 34]. b) Σ∠[CN(3)C, CN(3)P] = 339.8°: C(17)–N(3)–C(19) 111.7(6), P–N(3)–
C(17) 114.3(6), P–N(3)–C(19) 113.8(5). c) Σ∠[CN(3)C, CN(3)P] = 348.1°: C(17)–N(3)–C(19) 113.9(5), P–N(3)–C(17) 117.7(4), P–N(3)–C(19)
116.5(4). d) Data for one of two independent molecules in the unit cell. e) Σ∠[CN(3)C, CN(3)P] = 347.4°: C(17)–N(3)–C(19) 113.8(4), P–
N(3)–C(17) 117.4(3), P–N(3)–C(19) 116.2(3). f) Mean deviation from plane.
790
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 784–794

1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]erferrocenophanes
resulting oil was dissolved in hexane (10 mL). Insoluble materials
were separated by centrifugation, and the clear liquid was collected.
The solvent was removed in vacuo to give 360 mg (97 %) of 8a as a
yellow, oily-material. 1H NMR (250.1 MHz, CD2Cl2, 23 °C): δ = 0.23
Conclusions
1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophane
derivatives containing PIII or PV are accessible, after optimiza-
tion of known synthetic strategies. They were structurally char-
acterized in solution and in the solid state. In the solid state,
the surroundings of the nitrogen atoms in the exocyclic dieth-
ylamino group are pyramidal in all three cases studied. In all
derivatives, the reactivity of the N–Si bonds is surprisingly
high. In particular, the 2-diethylamino derivative appears to be
attractive for studying exchange reactions as well as ligand
properties in transition metal complexes.
4
2
[d, 18 H, Me3Si, J(31P,1H) = 1.4, J(29Si,1H) = 6.6 Hz], 1.18 [d, 9 H,
3
tBu, J(31P,1H) = 13.7 Hz], 3.81 (m, 2 H, H5,5'), 3.89 (m, 2 H, H3,3'),
3.94 (m, 2 H, H2,2'), 4.02 (m, 2 H, H4,4'). EI-MS (70 eV) for
C20H35N2PSi2Fe (446.14): m/z (%) = 446 (6) [M+], 389 (75) [M+–
C4H9], 317 (10) [M+–(C4H8 + SiMe3)], 73 (75), 57 (25).
1,3-Bis(trimethylsilyl)-2-tert-butyl-1,3,2-diaza-thiophosphoryl-
[3]ferrocenophane (8c): A solution of 8a (120 mg, 0.27 mmol) in
toluene (5 mL) was added at room temperature to an excess of pure,
degassed elemental sulfur (30 mg). The solution was stirred for 24 h
and afterwards filtered to remove most of the unreacted sulfur. The
solvent was removed in vacuo, and the resulting solid was dissolved
in hexane (15 mL). After filtration, the solvent was removed in vacuo
to give 112 mg (87 %) of 8c as a yellow solid. Single yellow crystals
of 8c suitable for X-ray diffraction were grown from hexane solution
after 4 weeks at –30 °C (m.p. 166–169 °C). 1H NMR (250.1 MHz,
Experimental Section
General
All syntheses and the handling of the samples were carried out observ-
ing necessary precautions to exclude traces of air and moisture. Care-
fully dried solvents and oven-dried glassware were used throughout.
1,1'-Bis(trimethylsilylamino)ferrocene, fc(NHSiMe3)2 (2) [5], and the
dilithiated species fc(NSiMe3)2Li2 (6) [11b] were prepared according
to the published procedure. Other starting materials were purchased
from Aldrich [butyllithium (1.6 m in hexane), dibutylmagnesium
(1.0 m in heptane), tBuPCl2, Et2NPCl2], Acros (PhOPCl2) and
Me3SiOOSiMe3 (ABCR), and used as received. NMR measurements:
Bruker ARX 250: 1H, 13C, 31P, 77Se, 15N, and 29Si NMR spectra [refo-
cused INEPT [40] based on 2J(29Si,1H) = 7 Hz] NMR; Varian INOVA
400: 1H, 13C, 31P, 29Si NMR spectra; chemical shifts are given with
respect to SiMe4 [δ1H (CHCl3/CDCl3) = 7.24; (CDHCl2) = 5.33; δ13C
(CDCl3) = 77.0; (CD2Cl2) = 53.8, δ = 29Si = 0 for Ξ(29Si) =
19.867184 MHz]; external aqueous H3PO4 (85 %) [δ31P = 0 for
Ξ(31P) = 40.480747 MHz], external neat MeNO2 [δ15N = 0 for
Ξ(15N) = 10.136767 MHz]. The assignments of 1H and 13C NMR spec-
troscopic signals are based on 1H-1H-NOE difference [32], and 2D 1H/
13C gHSQC experiments [33]. EI-MS spectra: Finnigan MAT 8500
spectrometer (ionization energy 70eV) with direct inlet, the m/z data
refer to the isotopes 1H, 12C, 14N, 56Fe, 28Si, 32S and 80Se. The melting
points (uncorrected) were determined with a Büchi 510 melting point
apparatus.
2
CD2Cl2, 23 °C): δ = 0.37 [s, 18 H, Me3Si, J(29Si,1H) = 6.5], 1.41 [d,
9 H, tBu, 3J(31P,1H) = 18.2 Hz], 3.81 (m, 2 H, H5,5'), 4.02 (m, 2 H,
H3,3'), 4.07 (m, 2 H, H2,2'), 4.14 (m, 2 H, H4,4'). EI-MS (70 eV) for
C20H35N2Si2PSFe (478.1): m/z (%) = 478 (85) [M+], 421 (100) [M+ –
C4H9], 389 (10) [M+ – (C4H9 + S)], 315 (55) [M+ – (C4H9 + SiMe3 +
S)], 270 (15), 244 (20), 73 (75).
1,3-Bis(trimethylsilyl)-2-tert-butyl-1,3,2-diaza-selenophosphoryl-
[3]ferrocenophane (8d): A solution of 8a (120 mg, 0.27 mmol) in
toluene (5 mL) and hexane (10 mL) was added at room temperature
to an excess of pure, degassed elemental selenium (30 mg,
0.38 mmol). The solution was stirred for 48 h to give a mixture con-
taining 8d (about 50 %) and 8a (about 50 %). The reaction mixture
decomposes slowly in CD2Cl2 at room temperature to give a mixture
containing 8d (about 60 %), 8a (about 15 %), and 12 (about 25 %)
(after 5 days) (31P NMR). 8d: 1H NMR (250.1 MHz, CD2Cl2, 23 °C):
δ = 0.43 [s, 18 H, Me3Si, 2J(29Si,1H) = 6.6 Hz], 1.43 [d, 9 H, tBu,
3J(31P,1H) = 18.9 Hz], 3.82, 4.04, 4.08 and 4.15 (all m, 2 H, 2 H, 2 H,
2 H, H2–5,2'–5').
1-tert-Butyl(chloro)phosphino-6-trimethylsilylaminoferrocene
(11): Method A: Freshly prepared fc(NSiMe3)2Li2 (6) (272 mg,
0.73 mmol) was taken up in hexane (30 mL), the suspension was
cooled to –70 °C, and tBuPCl2 (116 mg, 0.73 mmol) dissolved in hex-
ane (5 mL) was injected slowly through a syringe. After stirring the
reaction mixture for 1 h at –70 °C and afterwards for 1 h at ambient
temperature, insoluble materials were separated by centrifugation, and
the clear liquid was collected. The solvent was removed in vacuo to
give 263 mg of a mixture containing 8a (about 10 %) and 11 (about
90 %). The product 11 decomposes slowly at room temperature in
CD2Cl2 to give 3a [8] (after 7 d), Me3SiOSiMe3, and Me3SiCl.
Syntheses
fc(NSiMe3)2Mg(THF)2 (7): A solution of fc(NHSiMe3)2 (2) (422 mg,
1.17 mmol) in THF (10 mL) was cooled (–70 °C), and Bu2Mg was
added (1.2 mL of a 1.0 m solution in heptane, 1.2 mmol). The reaction
mixture was stirred at –70 °C for 30 h, afterwards allowed to reach
ambient temperature and kept stirring for further 30 min. The red solu-
tion was concentrated to 2–3 mL, afterwards hexane (20 mL) was
added and the mixture was cooled to –30 °C for 15 h. A brown precipi-
tate formed, which was separated using a centrifuge and decanting the
supernatant liquid. The solid was dried under vacuum to give 411 mg
(67 %) of 7 as a brown powder.
Method B: A suspension of fc(NSiMe3)2Mg(THF)2 (7) (360 mg,
0.68 mmol) in toluene (20 mL) was cooled to –70 °C, and tBuPCl2
(109 mg, 0.68 mmol) dissolved in toluene (3 mL) was injected slowly
through a syringe. After stirring the reaction mixture for 1 h at –70 °C,
the mixture was warmed to room temperature and afterwards for 16 h
1,3-Bis(trimethylsilyl)-2-tert-butyl-1,3,2-diazaphospha-
[3]ferrocenophane (8a): Freshly prepared fc(NSiMe3)2Li2 (6) at ambient temperature. Volatile materials were removed in vacuo, and
(309 mg, 0.83 mmol) was taken up in hexane (20 mL), the suspension hexane (30 mL) was added. The mixture was separated by centrifuga-
was cooled to –70 °C, and tBuPCl2 (132 mg, 0.83 mmol) dissolved in tion from insoluble materials, the liquid was collected, and the solvent
hexane (3 mL) was injected slowly through a syringe. After stirring was removed in vacuo to give of a mixture containing 11 (about 80 %)
1
the reaction mixture for 1 h at –60 °C and afterwards for 18 h at and 3a [8] (about 20 %). 11: H NMR (250.1 MHz, CD2Cl2, 23 °C):
ambient temperature, volatile materials were removed in vacuo and the δ = 0.22 (s, 9 H, Me3SiNH), 0.44 [d, 9 H, Me3Si, 4J(31P,1H) = 2.1 Hz],
Z. Anorg. Allg. Chem. 2010, 784–794
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
791

B. Wrackmeyer, E. V. Klimkina, W. Milius
ARTICLE
0.81 [d, 9 H, tBu, 3J(31P,1H) = 14.8 Hz], 2.41 (s, 1 H, NH), 3.67, 3.76, [D8]toluene, 23 °C): δ = 0.47 (s, 18 H, Me3Si), 3.72, 3.78, 3.96 and
1
3.87 and 4.59 (br) (all m, 1 H, 3 H, 3 H, 1 H, H2–5,7–10).
4.01 (all m, 2 H, 2 H, 2 H, 2 H, H2–5,2'–5'), 6.80–7.40 (m, 5 H, Ph). H
NMR (250.1 MHz, CD2Cl2, 23 °C): δ = 0.35 (s, 18 H, Me3Si), 4.02
(m, 6 H, H2,3,5,2',3',5'), 4.14 (m, 2 H, H4,4'), 7.16 (m, 1 H, Hp), 7.23 (m,
2 H, Hm), 7.35 (m, 2 H, Ho).
1,3-Bis(trimethylsilyl)-2-phenoxy-1,3,2-diazaphospha-
[3]ferrocenophanes (9a): Freshly prepared fc(NSiMe3)2Li2 (6)
(162 mg, 0.44 mmol) was taken up in hexane (20 mL), the suspension
was cooled to –60 °C, and PhOPCl2 (85 mg, 0.062 mL, 0.44 mmol)
dissolved in hexane (5 mL) was injected slowly through a syringe.
After stirring the reaction mixture for 1 h at –60 °C and afterwards
for 1 h at ambient temperature, insoluble materials were separated by
centrifugation, and the clear liquid was collected. Volatile materials
were removed in vacuo and the resulting oil was dissolved in hexane
(10 mL). After centrifugation the solvent was removed in vacuo to
give 110 mg (52 %) of 9a as a yellow, oily-material. 1H NMR
(250.1 MHz, [D8]toluene, 23 °C): δ = 0.26 [s, 18 H, Me3Si,
2J(29Si,1H) = 7.4 Hz], 3.81 (m, 2 H, H2,2'), 3.86 (m, 2 H, H3,3'), 4.06
(m, 2 H, H4,4'), 4.17 (m, 2 H, H5,5'), 6.84 (m, 1 H, Ph), 6.95–7.20 (m,
4 H, Ph). EI-MS (70 eV) for C22H31N2PSi2OFe (482.11): m/z (%) =
482 (30) [M+], 389 (100) [M+ – OC6H5], 316 (10) [M+ – (OC6H5 +
SiMe3)], 73 (75).
1,3-Bis(trimethylsilyl)-2-diethylamino-1,3,2-diazaphospha-
[3]ferrocenophane (10a): Method A: Freshly prepared
fc(NSiMe3)2Li2 (6) (207 mg, 0.56 mmol) was taken up in hexane
(20 mL), the suspension was cooled to –70 °C, and Et2NPCl2 (97 mg,
0.56 mmol) was injected slowly through a syringe. The mixture was
warmed to room temperature and kept stirring for 15 h. Insoluble mate-
rials were filtered off, the solvent was removed in vacuo, and the re-
sulting oil was dissolved in hexane (15 mL). After filtration the solvent
was removed in vacuo to give 219 mg of a mixture containing 10a
(ca. 80 %) and some starting material fc(NHSiMe3)2 2 (ca. 20 %) as
a yellow, oily-material.
Method B: A suspension of fc(NSiMe3)2Mg(THF)2 (7) (411 mg,
0.78 mmol) in hexane (30 mL) and toluene (5 mL) was cooled to –
1,3-Bis(trimethylsilyl)-2-phenoxy-1,3,2-diaza-thiophosphoryl- 70 °C, and Et2NPCl2 (135 mg, 0.78 mmol) was injected slowly
[3]ferrocenophane (9c): A solution of 9a in [D8]toluene was added through a syringe. After stirring the reaction mixture for 1 h at –70 °C,
at room temperature to an excess of pure, degassed elemental sulfur the mixture was warmed to room temperature. Volatile materials were
(1.5 equiv.). The solution was stirred for 1.5 month (31P, 29Si NMR removed in vacuo, and hexane (25 mL) was added. The mixture was
control) to give a mixture containing 9c (about 50 %), 9a (about separated by centrifugation from insoluble materials, the liquid was
50 %), and several unidentified side products. The solution was filtered collected, and the solvent was removed in vacuo to give 207 mg
to separate most of the unreacted sulfur. The solvent was removed in (58 %) of 10a as a yellow oil. Single yellow crystals of 10a suitable
vacuo, and the resulting solid was dissolved in CD2Cl2 to give, after for X-ray diffraction were grown from hexane solution after 14 d at –
centrifugation from insoluble materials, a mixture containing 9c (about 30 °C (m.p. 110–112 °C). 1H NMR (250.1 MHz, CD2Cl2, 23 °C): δ =
70 %) and 5c [9] (about 30 %). Single yellow crystals of 9c suitable 0.23 [d, 18 H, Me3Si, 4J(31P,1H) = 1.7 Hz], 1.10 (t, 6 H, CCH3,
for X-ray diffraction were grown from CD2Cl2 solution after several 7.1 Hz), 2.84 [dq, 4 H, NCH2, 3J(31P,1H) = 7.1 Hz, 7.1 Hz], 3.68, 3.83,
months at –30 °C (m.p. 170–175 °C). 1H NMR (250.1 MHz, 3.92 and 4.03 (all m, 2 H, 2 H, 2 H, 2 H, H2–5,2'–5').
Table 4. Crystallographic data of the 1,3-bis(trimethylsilyl)-1,3,2-diazaphospha-[3]ferrocenophanes 8c, 9c, 10a, 10c and 10d.
8c
9c
10a
10c
10d
Formula
C20H35FeN2PSSi2
Orange prism
0.22 × 0.16 × 0.12
Orthorhombic
Pbcm
C22H31FeN2OPSSi2 C20H36FeN3PSi2
C20H36FeN3PSSi2
Orange prism
0.22 × 0.16 × 0.14
Triclinic
C20H36FeN3PSeSi2
Yellow platelet
0.27 × 0.18 × 0.08
Triclinic
Crystal
Orange prism
0.31 × 0.22 × 0.18
Monoclinic
P21/n
Yellow prism
0.18 × 0.12 × 0.08
Orthorhombic
P212121
Dimensions /mm
Crystal system
Space group
Lattice parameters
a /pm
¯
P1
¯
P1
972.57(19)
1457.9(3)
1707.0(3)
1044.0(2)
1231.3(3)
2023.8(4)
894.91(18)
1436.8(3)
1903.0(4)
1058.7(2)
1576.5(3)
1641.5(3)
71.65(3)
88.70(3)
79.46(3)
4
1057.4(2)
1586.8(3)
1642.8(3)
71.60(3)
88.92(3)
79.34(3)
4
b /pm
c /pm
α /deg
β /deg
101.57(3)
γ /deg
Z
4
4
4
Absorption coefficient μ /
0.883
0.847
0.790
0.840
2.171
mm–1
Diffractometer
Measuring Range ϑ /°
Reflections collected
STOE IPDS I (Mo-Kα, λ = 71,073 pm), graphite monochromator
2.4–28.1
19788
1.95–26.0
17232
3736
2.5–26.0
17216
1888
1.96–26.0
17817
3908
2.2–28.1
11481
4494
Independent reflections [I > 1510
2σ(I)]
Absorption correction
Refined Parameters
Nonea)
None
Numerical
244
Nonea)
Numerical
505
0.098 / 0.047
130
271
505
wR2/R1 [I > 2σ(I)]
0.099 / 0.047
0.113 / 0.046
0.091 / 0.052
0.00(4)
0.133 / 0.060
Absolute structure parameter
Max./min. Residual electron 0.511 / –0.221
0.606 / –0.227
0.342 / –0.239
0.500 / –0.316
0.589 / –0.315
density /e·pm–3·10–6
a) Absorption corrections did not improve the parameter set.
792 www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 784–794

1,3-Bis(trimethylsilyl)-1,3,2-diazaphospha-[3]erferrocenophanes
1,3-Bis(trimethylsilyl)-2-diethylamino-1,3,2-diaza-thiophosphoryl-
[3]ferrocenophane (10c): The synthesis was carried out as described
for 8c, starting from 91 mg (0.20 mmol) of 10a and excess of pure,
degassed elemental sulfur (32 mg), to give 85 mg (88 %) of 10c as a
yellow solid. Single yellow crystals of 10c for X-ray diffraction were
grown from hexane solution after 14 d at –30 °C (m.p. 155–160 °C).
1H NMR (250.1 MHz, [D8]toluene, 23 °C): δ = 0.51 [s, 18 H, Me3Si,
2J(29Si,1H) = 6.5 Hz], 1.07 (t, 6 H, CCH3, 7.2 Hz), 3.03 [dq, 4 H,
Acknowledgement
This work was supported by the Deutsche Forschungsgemeinschaft.
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3
NCH2, J(31P,1H) = 11.9 Hz, 7.2 Hz], 3.59 (m, 2 H, H5,5'), 3.70 (m, 2
H, H3,3'), 3.73 (m, 2 H, H2,2'), 4.00 (m, 2 H, H4,4'). 1H NMR
2
(250.1 MHz, CD2Cl2, 23 °C): δ = 0.38 [s, 18 H, Me3Si, J(29Si,1H) =
6.6 Hz], 1.25 (t, 6 H, CCH3, 7.1 Hz), 3.14 [dq, 4 H, NCH2, 3J(31P,1H) =
11.9 Hz, 7.1 Hz], 3.66 (m, 2 H, H5,5'), 3.92 (m, 2 H, H3,3'), 4.00 (m, 2
H, H2,2'), 4.11 (m, 2 H, H4,4'). EI-MS (70 eV) for C20H36N3Si2PSFe
(493.1): m/z (%) = 493 (100) [M+], 478 (60) [M+ – CH3], 421 (20)
[M+ – NEt2], 389 (15) [M+ – (NEt2 + S)], 348 (10) [M+ – (NEt2
SiMe3)], 315 (45) [M+ – (2SiMe3 + S)], 271 (8), 258 (5), 73 (45).
+
1, 3-Bis(trimethylsilyl)-2-diethylamino-1, 3, 2-diaza-
selenophosphoryl-[3]ferrocenophane (10d): The selenide 10d was
prepared in the same way as described for 8d; the solution was stirred
for 2 d. The selenide was obtained in 70 % yield along with some of
[6] a) G. R. Knox, Proc. Chem. Soc. London 1959, 56–57; b) G. R.
Knox, P. L. Pauson, J. Chem. Soc. 1961, 4615–4618; c) A. N.
Nesmeyanov, V. N. Drozd, V. A. Sazonova, Dokl. Akad. Nauk
SSSR 1963, 150, 321–324.
the starting material fc(NHSiMe3)2 (2) as a yellow solid. Single yellow [7] A. Shafir, M. P. Power, G. D. Whitener, J. Arnold, Organometal-
lics 2000, 19, 3978–3982.
crystals of 10d for X-ray diffraction were grown from hexane solution
after 7 d at –30 °C (m.p. 166–170 °C). 1H NMR (250.1 MHz,
[8] B. Wrackmeyer, E. V. Klimkina, W. Milius, Inorg. Chem. Com-
mun. 2004, 7, 884–888.
2
[D8]toluene, 23 °C): δ = 0.57 [s, 18 H, Me3Si, J(29Si,1H) = 6.6], 1.09
[9] B. Wrackmeyer, E. V. Klimkina, W. Milius, Z. Naturforsch. 2009,
64b,, 1401–1412.
(t, 6 H, CCH3, 7.2 Hz), 3.03 [dq, 4 H, NCH2, 3J(31P,1H) = 12.3 Hz,
7.2 Hz], 3.57, 3.72, 3.74 and 3.99 (all m, 2 H, 2 H, 2 H, 2 H, H2–5,2'–5').
1H NMR (250.1 MHz, CDCl3, 23 °C): δ = 0.43 [s, 18 H, Me3Si,
2J(29Si,1H) = 6.6], 1.27 (t, 6 H, CCH3, 7.1 Hz), 3.18 [dq, 4 H, NCH2,
3J(31P,1H) = 12.1 Hz, 7.1 Hz], 3.67, 3.95, 4.03 and 4.16 (all m, 2 H, 2
H, 2 H, 2 H, H2–5,2'–5'). EI-MS (70 eV) for C20H36N3Si2PFeSe (541.1):
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m/z (%) = 541 (100) [M+], 526 (70) [M+ – CH3], 421 (29) [M+
–
NEt2], 389 (45) [M+ – (NEt2 + Se)], 316 (100) [M+ – (NEt2 + SiMe3
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1,3-Bis(trimethylsilyl)-2-hydro-1,3,2-diaza-phosphoryl-
[3]ferrocenophane (14): Bis(trimethylsilyl)peroxide (0.11 mL,
90 mg, 0.51 mmol) was added to a solution of 10a (57 mg,
0.12 mmol) in hexane (20 mL) at –20 °C. After standing for 48 h at
room temperature the solvent was removed in vacuo to give a mixture
containing 10a (about 25 %), 13 (about 25 %) and 14 (about 50 %).
The mixture was dissolved in hexane (20 mL), insoluble materials
were filtered off and the solvent was removed in vacuo to give 14
(together with several unidentified side products, about 30 % accord-
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1
ing to NMR spectra) as a yellow oil (15 mg). H NMR (250.1 MHz,
CD2Cl2, 23 °C): δ = 0.24 (s, 18 H, Me3Si), 3.77, 4.02, 4.13 (m, m, m,
1
2 H, 4 H, 2 H, H2–5,2'–5'), 7.48 [d, 1 H, PH, J(31P,1H) = 595.1 Hz].
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Crystal Structure Determinations of the 1,3-Bis(trimethylsilyl)-2-R-
1,3,2-diazaphospha-[3]ferrocenophanes 8c, 9c, 10a, 10c, and 10d
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Details pertinent to the crystal structure determinations are listed in
Table 4. Crystals of appropriate size were sealed under argon in Linde-
mann capillaries and the data collections were carried out at 20 °C
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Supporting Information (see footnote on the first page of this article):
Exchange reactions of the phosphine 10a, which lead to compounds
15 and 16.
Z. Anorg. Allg. Chem. 2010, 784–794
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
793

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Received: October 19, 2009
Published Online: January 28, 2010
794
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 784–794