1,3,2-diazaphospha-[3]ferrocenophanes. Molecular structures and multinuclear magnetic resonance studies

Article abstract of DOI:10.1515/znb-2009-11-1222

2-Phenoxy-1,3,2-diazaphospha-[3]ferrocenophane and related derivatives (oxide, sulfide, selenide) were prepared, characterized in solution by multinuclear magnetic resonance methods (1D and 2D ¹H, ¹³C, ¹⁵N and ³¹

Full text of DOI:10.1515/znb-2009-11-1222

1,3,2-Diazaphospha-[3]ferrocenophanes. Molecular Structures and
Multinuclear Magnetic Resonance Studies
Bernd Wrackmeyer, Elena V. Klimkina, and Wolfgang Milius
Laboratorium fu¨r Anorganische Chemie, Universita¨t Bayreuth, D-95440 Bayreuth, Germany
Reprint requests to Prof. Dr. B. Wrackmeyer. E-mail: b.wrack@uni-bayreuth.de
Z. Naturforsch. 2009, 64b, 1401 – 1412; received July 11, 2009
Dedicated to Professor Hubert Schmidbaur on the occasion of his 75th birthday
2-Phenoxy-1,3,2-diazaphospha-[3]ferrocenophane and related derivatives (oxide, sulfide, selenide)
were prepared, characterized in solution by multinuclear magnetic resonance methods (1D and 2D
1H, 13C, 15N and 31P NMR) and in the solid state by X-ray structural analysis. The conformation of
the 2-phenoxy derivative differs from that of the 2-tert-butyl compound. For further comparison, 2-R-
2,3-dihydro-1H-1,3,2-diazaphospha-phenalene derivatives R = tBu, PhO were prepared and studied
by the same NMR techniques. The molecular structure of a selenide was determined, and together
with the NMR evidence, it was concluded that the conformation of these heterocycles is independent
of the respective substituent at the phosphorus atom.
Key words: Aminophosphanes, 1,1ꢀ-Diaminoferrocene, [3]Ferrocenophanes, NMR Spectroscopy,
Crystal Structure
Introduction
aminophosphanes, only few examples with NH func-
tions have been studied since their preparation is of-
ten accompanied by numerous side reactions. If the or-
ganic backbone of the diamine and (or) the third sub-
stituent at phosphorus are sufficiently bulky such side
reactions may be less serious. However, experimental
solid-state molecular structures are scarce [7, 8], and
conclusive solution-state NMR data are either absent,
incomplete or wrong [7, 9, 10], in particular with re-
spect to the NH functions.
The multifaceted chemistry of phosphorus-nitrogen
compounds has attracted much attention for many
years [1], and the coordination number of phospho-
rus may range from 1 to 6. In most cases, the chem-
istry is concerned with phosphorus in the formal ox-
idation state P(III) or P(V), and frequently it is fairly
convenient to convert the P(III) into P(V) compounds
if they are the final target. Otherwise it is also easy
to start from a P(V) compound, if readily availabe, and
form the respective P–N bond by appropriate reactions.
Thus, aminophosphanes as P(III) compounds as well
as the corresponding P(V) compounds are well stud-
ied in many respects, including their molecular struc-
tures [2] and numerous NMR properties [3]. Cyclic
P-N compounds are of interest with respect to their
conformation and molecular dynamics which are most
efficiently studied by NMR spectroscopy, mostly by
1H, 13C and 31P NMR [3 – 6]. In the case of cyclic
1,1ꢀ-Diaminoferrocene (1) [11, 12] (Scheme 1)
is a potentially useful starting material to pre-
pare novel cyclic diaminophosphanes, since the
1,1ꢀ-ferrocenediyl group is bulky and may pro-
vide a fairly rigid backbone in 1,3,2-diazaphospha-
[3]ferrocenophanes. In a preliminary report [13], we
have disclosed the synthesis and molecular structures
of 2a and 2d, and it was pointed out that the 2-phenyl
derivative 3a may have a different structure as far as
the mutual orientation of the P–C and the N–H bonds
Scheme 1. 1,1ꢀ-Diaminofer-
rocene [11, 12] and four 1,3,
2-diazaphospha[3]ferroceno-
phanes reported in a prelimi-
nary study [13].
c
0932–0776 / 09 / 1100–1401 $ 06.00 ꢀ 2009 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
Table 1. 13C, 31P, 77Se and 1H NMR dataa,b of the 2-phenoxy-1,3,2-diazaphospha-[3]ferrocenophanes 4.
Compound
PR
4a
4c
4dd,e
4a
P–OPh
P(S)OPh
P(Se)OPh
P(O)OPh
δ
δ
31P
132.1
73.9
71.3 [888.8]
120.3 (6.4) Co
125.1 (< 0.5) Cp
130.1 (< 0.5) Cm
152.0 (6.2) Ci
91.4 (12.9)
70.3 (3.6)
67.2 (br)
69.3 (br)
64.0 (br)
19.9 (br)
13C(PR)
119.3 (9.7) Co
122.4 (< 0.5) Cp
129.7 (< 0.5) Cm
155.7 (9.0) Ci
93.9 (8.1)
120.3 (6.5) Co
124.9 (0.9) Cp
130.0 (< 0.5) Cm
151.8 (6.5) Ci
91.2 (10.6)
70.3 (4.6)
119.6 (6.0) Co
124.5 (< 0.5) Cp
129.9 (< 0.5) Cm
151.2 (5.8) Ci
89.4 (5.3)
69.9 (5.1)
66.9
68.4
63.4
4.27 {12.3}
δ
δ
δ
δ
δ
13C(fc-C1)
13C(fc-C2)
13C(fc-C3)
13C(fc-C4)
13C(fc-C5)
65.3 (< 0.5)c
65.5 (< 0.5)c
68.5 (< 0.5)c
69.6 (< 0.5)c
2.57 {+44.8}
67.1 (0.7)
69.1 (< 0.5)
63.7 (< 0.5)
3.46 {19.6}
([D8]toluene)
δ1H(NH)
4.23 {21.2}
a The assignment of the NMR signals is based on 1H-1H NOESY [26], and 2D 1H/13C gHSQC [19] experiments; b measured in [D8]toluene
(4a), CD2Cl2 (4c, 4d), CDCl3 (4b); coupling constants nJ(31P,13C) ( 0.5 Hz) are given in parentheses, 2J(31P,1H) in braces, 1J(77Se,31P)
c
in brackets; assignment might be reversed; d
δ
77Se = −292.8 [888.8]; for comparison: δ77Se (2d) = −186.4 [792.5] corrects a misprint in
ref. [13]; e 57Fe = 1115.1 (ref. [25]).
δ
are concerned. To the best of our knowledge, there
are no fully characterized cyclic diaminophosphanes
which differ in their principal conformation owing to
effects exerted by substituents at the phosphorus atom.
These properties might be of interest in further stud-
ies of such aminophosphanes as ligands in transition
metal chemistry. The question of alternative structures
raised previously [13] is addressed here in more detail,
including the 2-phenoxy group, by using multinuclear
1D and 2D magnetic resonance techniques, and by tak-
ing advantage of the results of X-ray structural analysis
for two further examples, in addition to those already
reported [13] for 2a and 2d.
Scheme 2. Reactions of 1,1ꢀ-diaminoferrocene (1) with
phenoxyphosphorus dichlorides towards 2-phenoxy-1,3,2-
diazaphospha-[3]ferrocenophanes.
Results and Discussion
Synthesis
firmed by various more sophisticated NMR experi-
ments (vide infra).
The synthesis of 4a, c, d (Scheme 2) followed
the conventional method reported for 2a – 2d [13],
whereas 4b was prepared by using the phenoxyphos-
phoryl dichloride by an analogous procedure as de-
scribed for 4a. These bulky aminophosphanes are of
low reactivity, except for hydrolysis, since the reac-
tion of neither 2a (Et2O, 4 d, r. t.) nor 4a (toluene,
The crude product from the reaction to give 4a
contained in repeated experiments a small amount of
about 2 % of a second defined compound, for which
the structure of the diastereomers 5/5ꢀ is proposed,
as indicated by 31P NMR spectra (see Experimen-
tal and Ref. [13] for the corresponding P-tBu com-
pounds).
◦
20 h at r. t., 1 h at 70 C) with trimethylsilyl azide
failed to afford the corresponding P(V) compounds.
Compounds 4 were obtained in pure state as or-
ange crystalline solids or, without further purification,
as moisture-sensitive yellow-orange oils or yellow-
greenish solids. Their solution-state structures follow
from the consistent NMR data (Table 1 and Experi-
mental Section), and the conformation has been con-
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
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Table 2. 13C, 31P, 77Se and 1H NMR dataa of the 2-R-2,3-dihydro-1H-1,3,2-diazaphospha-phenalenes 6a, 6d, 7a and 7d.
δ
13C
C-6a
δ
31P
δ1H(NH)
6 (R = tBu)
6a
C-3a,9a
138.6
(6.1)
137.3
(5.8)
C-4,9
108.4
(< 0.5)
109.7
(7.4)
C-5,8
126.2
(0.5)
127.2
(1.3)
C-6,7
117.9
(< 0.5)
120.8
(< 0.5)
C-9b
115.6
(2.9)
113.4
(5.5)
CH3
24.2 (18.2)
P–C
38.2 (24.5)
134.9
(< 0.5)
135.4
(< 0.5)
71.3
5.06
P–tBu
6db
{+38.0}
24.9 (2.4)
44.3 (71.3)
70.6
(71.6)
[815.3]
5.60
P(Se)tBu
{12.6}
7 (R = OPh)
7a
C-3a,9a
135.5
(5.3)
135.6
(7.1)
C-4,9
108.9
(1.3)
110.4
(8.7)
C-5,8
127.0
(1.1)
127.1
(1.1)
C-6,7
119.7
(< 0.5)
121.6
(< 0.5)
C-6a
C-9b
108.9
(1.3)
115.1
(7.6)
Ci
Co
Cm
Cp
135.4
(< 0.5)
135.4
(0.8)
153.1
(3.2)
150.3
(9.2)
ꢁ1.6ꢂ
121.5
(6.8)
122.2
(4.2)
127.0
(1.1)
129.4
(2.1)
121.5
(6.8)
125.5
(2.4)
85.7
5.50
P–OPh
{+36.9}
7dc
P(Se)OPh
42.7
[928.5]
6.27
{14.3}
ꢁ1.6ꢂ
a
Measured in CD2Cl2 (6a, 6d), CDCl3 (7a, 7d); coupling constants nJ(31P,13C) ( 0.5 Hz) are given in parentheses, 3J(77Se,13C) in ꢁꢂ,
2J(31P,1H) in braces; 1J(77Se,31P) in brackets; b δ77Se = −251.7 [814.2]; c δ77Se = −268.7 [928.3].
Table 3. 15N NMR dataa of the 2-R-1,3,2-diazaphospha-[3]ferrocenophanes 2 – 4 and of the 2-R-2,3-dihydro-1H-1,3,2-
diazaphospha-phenalenes 6a, 6d, 7a and 7d.
Compound
PR
4a
4c
4d
2a
2b
2c
2d
3a
6a
6d
7a
7d
P–OPh P(S)OPh P(Se)OPh P–tBu P(O)t Bu P(S)tBu P(Se)t Bu P–Ph
P–tBu P(Se)tBu P–OPh P(Se)OPh
δ
15N
−328.8 −324.3 −320.6
−341.8 −341.4 −335.9 −335.0 −344.7 −323.6 −310.0 −295.6 −290.6
1J(31P,15N), Hz +72.2 6.8
3.5
−86.4
+78.2 n. o.
−71.1
27.0
–
29.7
−78.5
+72.8 +52.8 10.9
−86.7 −87.5
+60.2 5.5
−86.9 −88.9
1J(15N,1H), Hz −82.7 −86.1
–
–
a
Measured in [D8]toluene (4a), CD2Cl2 (4c, 4d, 6a, 6d, 2a, 2c, 3a), CDCl3 (7a, 7d, 2d), [D8]DMSO (2b); n. o. = not observed.
Scheme 3. Synthesis of 2-substituted
2,3-dihydro-1H-1,3,2-diazaphospha-
phenalene derivatives.
Two other cyclic diaminophosphanes 6a and 7a and NMR studies and calculations
their selenides 6d and 7d were prepared (Scheme 3)
1
In addition to H, 13C and 31P NMR data of the
[3]ferrocenophanes 4 (Table 1) and comparable 1,3,2-
diazaphospha-phenalene derivatives 6 and 7 (Table 2),
the 15N NMR parameters of 2, 4, 6 and 7 are of
interest (Table 3). The major question regarding the
solution-state structures of the 1,3,2-diazaphospha-
[3]ferrocenophanes concerns the mutual orientation of
the bond vectors of the P substituent and the N–H
bonds. In the case of 2a, 1H-1H NOE difference exper-
iments indicated syn orientation (see Scheme 1), the
same as determined by X-ray structural analysis [13].
Expectedly, this orientation did not change with oxida-
tion, as shown by the molecular structure of 2d [13].
Apparently, the magnitude of the coupling constants
for comparison of NMR spectroscopic properties (Ta-
ble 2), and in the case of the selenide 6d, the
molecular structure was determined by single crys-
tal X-ray diffraction (vide infra). The molecular struc-
ture of 2-ethoxy-2,3-dihydro-1H-1,3,2-diazaphospha-
phenalene 8a has been reported [7a], the ethoxy
group being in anti position (as the phenoxy group
in 4) relative to the N–H bonds. In contrast with
the [3]ferrocenophanes 2a and 4a, which possess dif-
ferent ring conformations, the corresponding 1,3,2-
diazaphospha-phenalene derivatives 6a and 7a [7a, 14]
appear to have alike conformations, most likely
the one which was determined in the solid state
for the 2-ethoxy derivative 8a [7a]. This assump-
tion is further confirmed by the molecular structure
of 6d.
| J(31PN1H)| serves as an unambiguous criterion to de-
2
cide between the alternative solution-state structures of
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
Fig. 1. Contour plot of the 25.4 MHz 1H/15N heteronuclear shift correlation (HMQC, refocused) for 2a and 4a (both in
CD2Cl2 at 23 ◦C). Note the positive and negative tilt of the cross peaks for 2a and 4a, respectively (see text).
Fig. 2. (A) 40.5 MHz 15N/1H heteronuclear shift correlation (gHSQC [19] with 15N decoupling in F1) of 2d (CDCl3 at 23 ◦C).
(B) The results of the corresponding 1D experiment with (upper trace) and without 15N decoupling (lower trace).
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
1405
the P(III) compounds 2a and 4a. This suggests that
the conformation of 2a is opposite from that of 4a.
It is known that in the case of comparable coupling
constants 2J(31P,13C) [15], magnitude and sign de-
pend on the analogous geometrical factors. Therefore,
1
2D H/15N inverse correlation experiments were per-
formed to compare the signs of the coupling constants
1J(31P,15N) and 2J(31PN1H) (Figs. 1 and 2).
For the correct interpretation of the results of such
experiments, the negative sign of the gyromagnetic ra-
tio γ(15N) must be considered, and it is more advis-
able to use the concept of reduced coupling constants
K(AB) = 4π2J(A,B) (γAγB h)−1. Thus, the positive tilt
of the cross peaks [16] in the 1H/15N correlation for 2a
1
Fig. 3. 101.3 MHz 31P{ H} NMR spectra (refocused IN-
EPT [◦27] with Hahn echo extension [22]) of 2d (CDCl3
at 23 C; Hahn echo delay 0.05 s). The 13C satellites for
nJ(31P,13C) are marked by arrows. The 15N satellites for
1J(31P,15N) are marked by asterisks.
1
proves alike signs of K(31P,15N) and 2K(31PN1H),
whereas the analogous experiment for 4a reveals op-
posite signs, indicated by the negative tilt of the cross
peaks. Since K(31P,15N) in aminophosphanes is in- and deserve more attention. In general, 31P NMR sig-
variably negative [17, 18], it follows that 2K(31PN1H) nals of P-N compounds are more or less severely
in 2a is relatively small and negative, in contrast with broadened owing to partially relaxed (unresolved) 31P-
1
large and positive K(31PN1H) in 4a. Since both gy- 14N spin-spin coupling, and the broadening depends
2
romagnetic ratios γ(31P) and γ(1H) are > 0, the signs on the number of 14N nuclei linked to 31P, the mag-
1
of 2K and 2J are the same.
nitude of J(31P,14N) and the quadrupole-induced nu-
clear spin relaxation times [TQ(14N)]. In order to re-
duce the relative intensity of the central 31P NMR sig-
nal, it has been proposed to enhance the 31P magneti-
zation by polarization transfer and extend this pulse se-
quence by a Hahn echo with appropriate delays (HEED
experiments) [22]). This is most effective if there is
only one 14N linked to the 31P nucleus. However, it
also can help to reduce the line width of the 31P NMR
signal of an 14N-31P-15N isotopomer, and therefore al-
lows to detect the 15N satellites more readily, as shown
in Fig. 3, where the 15N satellites are somewhat less
broad, and their height is similar even greater than for
13C satellites, in spite of the three-times lower natural
abundance of 15N.
In the cases of the P(V) compounds in the se-
ries 2 or 4, the magnitude of the coupling constants
2
| J(31PN1H)| is less diagnostic, considering that they
are small and may be of either sign, as is frequently
observed for geminal coupling constants. Although the
2D 15N/1H correlation experiment for 2d in Fig. 2
proves opposite signs of 1K(31P,15N) and 2K(31PN1H)
(negative tilt of the cross peaks), this result is less
straightforward to analyze in a general way, since the
sign of 1K(31P,15N) may be negative or positive in
P(V)-N compounds [17, 18].
1
A sample of 2d was selected to analyze the 31P{ H}
NMR spectrum for satellites (Fig. 3) due to spin-
spin coupling of 31P with spin-1/2 nuclei other than
1H. In the case of 77Se, this is more of a routine
The proposed conformation of the 1,3,2-diaza-
phospha-phenalene derivatives 6 and 7 in solution fol-
lows from 1H-1H NOE difference experiments. A typi-
cal example is shown in Fig. 4 for 7d. There is no NOE
1
nature, and many data J(77Se,31P) are listed in the
literature [20]. Of course, information on coupling
n
constants J(31P,13C) are also readily obtained from
1
1
13C{ H} NMR spectra, although the measurements
for the H(OPh) NMR signals upon irradiation of the
1H(NH) transitions and vice versa, whereas an NOE
of these data from 31P NMR spectra may be an al-
ternative, in particular if isotope-induced chemical
is observed for the Hortho(OPh) NMR signals (along
1
1
n
shifts [21] ∆12/13C(31P) are of interest. In the case
with the expected strong NOE for the H(NH) and of
1
of 1J(31P,15N), the measurement of 15N NMR spectra
sometimes may be time consuming, whereas an excel-
lent signal-to-noise ratio in 31P NMR spectra is read-
other H(CH-phenalene) NMR signals) upon irradia-
tion of the 1H4,9 transitions.
The calculations [24] of both sign and magnitude
ily accomplished. Moreover, isotope-induced chemical of the coupling constants 2J(31PN1H) for the opti-
shifts 1∆14/15N(31P) cover a fairly large range [22, 23] mized geometries of the model compounds 9M(syn)
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
Fig. 4. 399.8 MHz 1H-1H NOE
difference spectra (gradient en-
hanced [26]) of 7d (in CD2Cl2
◦
at 23 C; relaxation delay 2.0 s;
mixing time 0.9 s). (A) Normal
1H NMR spectrum. (B) Irradia-
tion of 1H4,9; response: 1H(NH),
1H5,8, 1H6,7, and 1Hortho(OPh).
Fig. 5. Optimized geometries (B3LYP/6-
311+G(d,p) [24]) of the 1,3,2-diazaphosph-
orinanes 9M, together with calculated coupling
constants 2J(31PN1H) [24].
and 9M(anti) is in complete agreement with the ex- chains, of which one is picked out in part in Fig. 7.
perimental findings (Fig. 5). It is of interest to note The structural data of 4a and 2a are well comparable
that the magnitude of 1J(31P,15N), in contrast with except for the different conformation. The anti orienta-
2J(31PN1H), is hardly affected by the different con- tion of P–OPh and N–H bonds in 4a enforces widening
formations. This has been noted previously for some of the bond angles P–N–C(1,6) (127.0(3)◦, 125.9(2)◦),
non-cyclic aminophosphanes [3b].
in contrast to the syn conformation of P–tBu and N–H
bonds in 2a (115.0(4)◦, 113.4(4)◦). Oxidation of phos-
phorus to give 4b causes the usual changes in bond
lengths and angles in the surroundings of the phospho-
rus atom.
Solid-state structural studies of the 2-phenoxy-1,3,2-
diazaphospha-[3]ferrocenophanes 4a, 4b and 2-tert-
butyl-2,3-dihydro-1H-1,3,2-diazaselenophosphoryl-
phenalene 6d
The molecular structure of 6d (Fig. 8; see Table 5 for
structural parameters) shows that N–H bonds and the
The molecular structures of 4a and 4b are shown in P-tBu group are in anti-position, which is most likely
Fig. 6, and selected structural parameters are given in true also for the P(III) compound 6a, in agreement
Table 4, together with data for 2a for comparison. In with the findings for the N–H bonds and the P-OEt
the case of 4a, intermolecular interactions are weak or group in 8a [7a]. It is therefore concluded that this
negligible, whereas the molecules of 4b are linked by particular conformation is usually observed irrespec-
N–H···O hydrogen bonds in slightly different zig-zag tive of the substituent at the phosphorus atom. Thus,
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
1407
Fig. 6. Molecular structures of 4a
(left) and 4b (right) in the solid state
(ORTEP, 40 % probability ellipsoids;
hydrogen atoms (except NH) omit-
ted for clarity). For selected distances
and angles see Table 5.
Table 4. Selected bond lengths (pm) and angles (deg)a of the
2-phenoxy-1,3,2-diazaphospha-[3]ferrocenophanes 4a, 4b,
and of the 2-tert-butyl-1,3,2-diazaphospha-[3]ferrocenoph-
ane 2ab for comparison.
4a
R = OPh
4bc
R = OPh
E = O
2a
R = tBu
P–N(1)
P–N(2)
P–O
C(1)–N(1)
C(6)–N(2)
P–O(1)
169.4(3)
170.0(3)
166.1(3)
141.3(5)
139.8(6)
162.5(3)
161.4(3)
159.6(3)
142.6(4)
143.4(4)
146.3(2)
267.5
P–N(1)
P–N(2)
P–C(11)
C(1)–N(1)
C(6)–N(2)
172.1(5)
174.4(4)
185.9(6)
142.7(7)
143.1(6)
N(1)···N(2)
272.3
307.4
N(1)···N(2)
C(1)···C(6)
274.3
312.3
C(1)···C(6)
308.2
N(1)–P–N(2) 106.68(16) 111.40(16) N(1)–P–N(2) 104.7(2)
N(1)–P–O
N(2)–P–O
N(1)–P–O(1)
N(2)–P–O(1)
100.13(17) 107.30(15) N(1)–P–C(11) 101.8(2)
94.44(16) 100.68(15) N(2)–P–C(11) 101.4(2)
111.95(15)
112.19(16)
P–N(1)–C(1) 127.0(3)
P–N(2)–C(6) 125.9(2)
124.4(2)
124.2(2)
127.5(3)
112.73(15)
9.1
4.6
4.8
P–N(1)–C(1) 115.0(4)
P–N(2)–C(6) 113.4(4)
Fig. 7. View of the arrangement of molecules of 4b
in the crystal lattice (ball and stick model), showing
close intermolecular contacts: N(1A)···O(1C) 302.9 pm,
O(1C)···H(1A) 219.1 pm, N(1A)–H(1A)–O(1C) 164.5◦;
N(2A)···O(1D) 286.3 pm, O(1D)···H(2A) 205.7 pm,
N(2A)–H(2A)–O(1D) 155.6◦. The second independent ar-
rangement of 4b is similar, and in both cases, no hydrogen
bonds are present between the zig-zag chains.
P–O–C(11)
O(1)–P–O(2)
C5 / C5 (α)
124.5(3)
9.2
C5 / C5 (α)
8.9
C5 / N(1) (β1) 4.5
C5 / N(2) (β2) 2.1
C5 / N(1) (β1) 5.5
C5 / N(2) (β2) 1.8
towards
iron
towards
iron
towards
iron
C5-Fe-C5 (γ) 172.4
173.7
0.1
C5-Fe-C5 (γ) 171.9
Conclusions
C5 / C5
0.3
C5 / C5
0
(twist) (τ)
(twist) (τ)
1,3,2-Diazaphospha-[3]ferrocenophanes are unique
cyclic diaminophosphanes, since they exist in solution
and in the solid state in different conformations, de-
pending on the bulkiness of the substituent at the phos-
phorus atom, as shown by determination of the struc-
ture in solution by various 1D and 2D NMR spectro-
a The definition of the angles α, β, γ and τ is given in refs. [25, 28];
b
ref. [13]; c one of two crystallographically independent molecules
selected.
the 1,3,2-diazaphospha-[3]ferrocenophane is a special
case, where a bulky substituent such as a tBu group at
the phosphorus atom prefers the steric repulsion by the scopic techniques and in the solid state by X-ray struc-
N-H groups over that exerted by the C-H units of the tural analysis. These conformations remain unchanged
after oxidation of the phosphorus atom.
ferrocenediyl group.
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1408
B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
Fig. 8. Two views of the molec-
ular structure of 6d in the solid
state (A: ORTEP, 40 % probabil-
ity ellipsoids; B: ball and stick
model; hydrogen atoms (except
NH) are omitted for clarity). See
Table 5 for structural parameters.
13C NMR signals are based on 1H-1H NOE difference [26],
and 2D 1H/13C gHSQC experiments [19]. For special pur-
Table 5. Selected bond lengths (pm) and angles (deg) of
2-tert-butyl-2,3-dihydro-1H-1,3-diaza-2-selenophosphoryl-
phenalene 6d and of 2-ethoxy-2,3-dihydro-1H-1,3,2-
diazaphospha-phenalene 8a (ref. [7a]) for comparison.
1
poses (see. Fig. 3), 31P{ H} NMR spectra were recorded us-
ing the refocused INEPT pulse sequence [27] extended by
an appropriate Hahn echo delay [22, 23f]. IR spectra: Perkin
Elmer Spectrum 2000 FTIR. EI-MS spectra: Finnigan MAT
8500 spectrometer (ionisation energy 70 eV) with direct in-
let, the m/z data refer to the isotopes 1H, 12C, 14N, 56Fe,
16O, 32S and 80Se. The melting points (uncorrected) were
determined using a Bu¨chi 510 melting point apparatus. All
calculations were carried out using the GAUSSIAN program
package [24].
6d
8a
R = tBu
R = OEt
170.1(4)
167.4(5)
P–N(1)
P–N(2)
P–Se
C(1)–N(1)
C(9)–N(2)
P–C(11)
N(1)–P–N(2)
N(1)–P–C(11)
N(2)–P–C(11)
N(1)–P–Se
N(2)–P–Se
P–N(1)–C(1)
P–N(2)–C(9)
Se–P–C(11)
165.8(4)
165.7(4)
210.78(13)
140.9(5)
141.3(6)
184.1(5)
100.45(19)
108.3(2)
108.7(2)
112.35(15)
113.53(14)
126.1(3)
125.3(3)
112.79(16)
P–N(1)
P–N(2)
C(1)–N(1)
C(3)–N(2)
P–O
N(1)–P–N(2)
N(1)–P–O
N(2)–P–O
140.3(6)
140.8(6)
162.3(3)
95.1(2)
105.2(2)
105.9(2)
2-Phenoxy-1,3,2-diazaphospha-[3]ferrocenophane (4a)
A suspension of 1,1ꢀ-diaminoferrocene 1 (287 mg,
1.33 mmol) in Et2O (25 mL) together with triethylamine
(0.44 mL, 3.16 mmol) was prepared. The suspension was
cooled to 0 ◦C, and PhOPCl2 (259 mg, 1.33 mmol) dis-
solved in Et2O (5 mL) was injected slowly through a sy-
ringe. The reaction mixture was stirred at 0 ◦C for 2 h; then it
was allowed to reach ambient temperature and kept stirring
for 20 h. Insoluble materials were filtered off, and volatile
materials were removed from the filtrate in vacuo. The re-
maining yellow solid was dissolved in Et2O (20 mL), and the
solution was filtered. After removing of the solvent in vacuo
the product 4a (287 mg; 64 %) was left as a yellow-orange
oily material (together with some 5/5ꢀ, < 2 %). Orange sin-
gle crystals of 4a suitable for X-ray diffracti◦on were grown
from toluene solution after 2 weeks at −20 C (m. p. 226 –
229 ◦C).
P–N(1)–C(1)
P–N(2)–C(3)
126.9(3)
128.5(4)
Experimental Section
General
All preparative work as well as handling of the samples
was carried out observing precautions to exclude traces of
air and moisture. Carefully dried solvents and oven-dried
glassware were used throughout. The deuterated solvents
CD2Cl2 and CDCl3 were distilled over CaH2 in an atmo-
sphere of argon. All other solvents were distilled from Na
metal in an atmosphere of argon. 1,1ꢀ-Diaminoferrocene (1)
was prepared according to the published procedure [12].
Triethylamine was distilled from Na prior to use. Other
starting materials were purchased from Aldrich (tBuPCl2)
or Acros (PhOPCl2, PhOP(O)Cl2), and used without fur-
ther purification. NMR measurements: Bruker ARX 250:
1H, 13C, 31P, 77Se, and 15N NMR; Varian INOVA 400:
1H, 13C, 31P NMR; Bruker DRX 500: 1H, 13C, 31P NMR;
chemical shifts are given with respect to SiMe4 [δ1H
(CHCl3/CDCl3) = 7.24; (CDHCl2) = 5.33; ((CDH2)2SO) =
2.50; δ13C (CDCl3) = 77.0; (CD2Cl2) = 53.8; ((CD3)2SO) =
39.4]; external aqueous H3PO4 (85 %) [δ31P = 0 for
4a: 1H NMR (250.1 MHz, [D8]toluene, 23 ◦C): δ = 2.57
(br. d, 2H, NH, 2J(31PN1H) = 44.8 Hz), 3.63, 3.84, 3.95 and
ꢀ
ꢀ
3.97 (all m, 8H, H2−5,2 −5 ), 6.86 (m, 1H, Ph), 7.00 – 7.25 (m,
4H, Ph). – 1H NMR (250.1 MHz, CD2Cl2, 23 ◦C): δ = 3.48
(br. d, 2H, NH, 2J(31PN1H) = 44.5 Hz), 3.99, 4.01 and 4.13
ꢀ
ꢀ
(all m, 2H, 4H, 2H, H2−5,2 −5 ), 7.10 (m, 1H, Ph), 7.20 – 7.45
(m, 4H, Ph).
◦
5: 31P NMR (101.3 MHz, CDCl3, 23 C): δ = 116.2 (d,
Ξ(31P) = 40.480747 MHz], external neat MeNO2 [δ15N = 1P, 2J(31P, 31P) = 394.2 Hz), 135.2 (d, 1P, 2J(31P, 31P) =
0 for Ξ(15N) = 10.136767 MHz]. The assignments of 1H and 394.2 Hz).
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B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
1409
Table 6. Crystallographic data of the 2-phenoxy-1,3,2-diazaphospha-[3]ferrocenophanes 4a, 4b and of 2-tert-butyl-2,3-
dihydro-1H-1,3-diaza-2-selenophosphoryl-phenalene 6d [29].
4a
4b
6d
Formula
C16H15FeN2OP
orange prisms
0.22×0.18×0.08
monoclinic
P21
C16H15FeN2O2P
yellow needles
0.25×0.18×0.08
monoclinic
P21/n
C14H17N2PSe
light-yellow rhombs
0.26×0.18×0.15
triclinic
Crystal
Dimensions, mm3
Crystal system
Space group
¯
P1
Lattice parameters
a, pm
b, pm
c, pm
606.91(12)
1257.7(3)
944.13(19)
90
99.34(3)
90
2
1.2
293
1805.5(4)
680.44(14)
2558.0(5)
90
106.73(3)
90
849.29(17)
918.20(18)
1079.2(2)
65.68(3)
71.60(3)
86.24(3)
2
α, deg
β, deg
γ, deg
Z
8
1.1
Absorption coefficient µ, mm−1
T, K
2.7
Diffractometer
Stoe IPDS I (MoKα , λ = 71.073 pm), graphite monochromator
Measuring range ϑ, deg
Reflections collected
Independent reflections [I ≥ 2σ(I)]
Absorption correction
Max. / min. transmission
Refined parameters
wR2/R1 [I ≥ 2σ(I)]
Absolute structure parameter
Max./min. residual electron density, e pm−3 ·10−6
a
2.2 – 28.1
6081
2.4 – 28.1
2.2 – 26.0
5395
2633
numerical
0.7672 / 0.5530
163
6918
3043
6918
nonea
nonea
–
190
–
397
0.103 / 0.043
0.01(2)
0.748 / −0.553
0.072 / 0.040
–
0.438 / −0.230
0.131 / 0.055
–
0.901 / −0.336
Absorption corrections did not improve the structure refinement.
5ꢀ: 31P NMR (101.3 MHz, CDCl3, 23 ◦C): δ = 118.7 (d, tion was stirred for 1.5 d, filtered, and the solvent was re-
1P, 2J(31P, 31P) = 345.9 Hz), 134.4 (d, 1P, 2J(31P, 31P) = moved in vacuo to give 82 mg (74 %) of 4d as a yellow
345.9 Hz).
solid (m. p. 165 – 174 ◦C, decomp.). – 1H NMR (250.1 MHz,
◦
CD2Cl2, 23 C): δ = 3.96, 4.05, 4.13 and 4.23 (all m, 8H,
2−5,2ꢀ−5ꢀ
H
), 4.23 (br. d, 2H, NH, 2J(31PN1H) = 21.2 Hz),
2-Phenoxy-1,3,2-diaza-thiophosphoryl-[3]ferrocenophane
(4c)
7.20 (m, 1H, Ph), 7.32 – 7.47 (m, 4H, Ph). – EI-MS (70 eV)
for C16H15N2OPSeFe (417.94): m/z (%) = 418 (100) [M]+,
324 (30) [M–C6H5OH]+, 244 (50) [M–C6H5OH–Se]+, 229
(14), 214 (12), 182 (10), 134 (18).
A solution of 4a (110 mg, 0.33 mmol) in CH2Cl2 (5 mL)
was added at r. t. to an excess of dry and degassed elemen-
tal sulfur (35 mg). The solution was stirred for 1 d and then
filtered to separate most of the unreacted sulfur. The solvent
was removed in vacuo, the remaining yellow-green solid was
dissolved in toluene (10 mL), and the solution was filtered.
The solvent was removed in vacuo to give 98 mg (81 %)
of 4c as a yellow-green solid (m. p. 160 – 165 ◦C, decomp.). –
1H NMR (250.1 MHz, [D8]toluene, 23 ◦C): δ = 3.45 (br. d,
2H, NH, 2J(31PN1H) = 19.2 Hz), 3.57, 3.73 and 3.80 (all
2-Phenoxy-1,3,2-diaza-phosphoryl-[3]ferrocenophane (4b)
A suspension of 1,1ꢀ-diaminoferrocene (1) (194 mg,
0.9 mmol) in Et2O (25 mL) together with triethylamine
(0.3 mL, 2.15 mmol) was cooled to −20 ◦C, and PhOP(O)Cl2
(189 mg, 0.9 mmol) dissolved in Et2O (3 mL) was injected
slowly through a syringe. The reaction mixture was stirred
at −20 ◦C for 2 h; then it was allowed to reach ambient tem-
perature and kept stirring for 1.5 d. Insoluble materials were
filtered off, and volatile materials were removed from the fil-
trate in vacuo. The remaining yellow solid was dissolved in
Et2O (20 mL) and toluene (10 mL), and the solution was fil-
tered. After removing of the solvent in vacuo the product 4b
(115 mg; 36 %) was left as a yellow-green solid. Orange sin-
ꢀ
ꢀ
m, 2H, 2H, 4H, H2−5,2 −5 ), 6.86 (m, 1H, Ph), 7.02 (m, 2H,
Ph), 7.37 (m, 2H, Ph). – EI-MS (70 eV) for C16H15N2OPSFe
(370.0): m/z (%) = 370 (100) [M]+, 290 (5), 276 (50) [M–
C6H5OH]+, 197 (10), 134 (10).
2-Phenoxy-1,3,2-diaza-selenophosphoryl-[3]ferroceno-
phane (4d)
A solution of 4a (90 mg, 0.27 mmol) in toluene (5 mL) gle crystals of 4b suitable for X-ray diffraction were grown
was added at room temperature to an excess of dry and de- from CH2Cl2 after 1 week at −30 ◦C (m. p. 235 – 250 ◦C, de-
1
◦
gassed elemental selenium (63 mg, 0.80 mmol). The solu- comp.). – H NMR (250.1 MHz, CDCl3, 23 C): δ = 4.02,
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1410
B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
ꢀ
ꢀ
4.08 and 4.20 (all m, 4H, 2H, 2H, H2−5,2 −5 ), 4.27 (br. d, 6.98 (m, 2H), 7.0 – 7.1 (m, 1H), 7.15 – 7.3 (m, 6H). – EI-MS
2H, NH, 2J(31PN1H) = 12.3 Hz), 7.15 (m, 1H, Ph), 7.30– (70 eV) for C16H13N2OP (280.08): m/z (%) = 280 (23) [M]+,
7.45 (m, 4H, Ph). – EI-MS (70 eV) for C16H15N2O2PFe 232 (7), 187 (100) [M–C6H5O]+, 186 (92) [M–C6H5OH]+,
(354.02): m/z (%) = 354 (100) [M]+, 274 (8), 260 (50) [M– 140 (9).
C6H5OH]+, 198 (15), 182 (12), 134 (15). IR (CHCl3): ν =
3390 (N–H) cm−1
The selenides 6d and 7d were prepared in the same way
as 4d, using toluene and ether, respectively, as the solvents.
Orange single crystals of 6d suitable for X-ray diffraction
were grown from CDCl3, at −30 ◦C (m. p. 245 – 250 ◦C).
.
2-tert-Butyl-2,3-dihydro-1H-1,3,2-diazaphospha-phenalene
(6a)
6d: 1H NMR (250.1 MHz, CD2Cl2, 23 ◦C): δ
=
1.19 (d, 9H, 3CH3, 3J(31P,1H) = 19.7 Hz), 5.60 (br. d,
2H, NH, 2J(31PN1H) = 12.6 Hz), 6.68 – 6.72 (dd, 2H,
6.4 Hz, 1.8 Hz), 7.05 – 7.13 (m, 4H). – EI-MS (70 eV)
for C14H17N2PSe (324.03): m/z (%) = 324 (15) [M]+, 267
(5) [M–(CH3)3C]+, 187 (100) [M–(CH3)3C–Se]+, 186 (37)
[M–(CH3)3CH–Se]+.
A
solution of 1,8-diaminonaphtalene (224 mg,
1.42 mmol) in toluene (15 mL) together with triethy-
lamine (0.45 mL, 3.2 mmol) was cooled to 0 ◦C, and
tBuPCl2 (225 mg, 1.42 mmol) dissolved in hexane (3 mL)
was injected slowly through a syringe. The reaction mixture
◦
was stirred at 0 C for 2 h, allowed to reach ambient tem-
◦
1
7d: (m. p. 170 – 173 C, decom.): H NMR (250.1 MHz,
perature and kept stirring for 20 h. Insoluble materials were
filtered off, and volatile materials were removed from the fil-
trate in vacuo. The resulting mixture contained 6a (ca. 70 %)
and some starting material (1,8-diaminonaphtalene) as
a crimson-colored material, a mixture of an oil with a
solid. 7a was obtained in the same way; the remaining
rose-white-colored solid was dissolved in hexane/CH2Cl2
(3 : 1.2), filtered off, and the solid was dried in vacuo to
give 7a as a white solid.
CDCl3, 23 C): δ = 6.27 (br. d, 2H, NH, 2J(31PN1H) =
◦
14.3 Hz), 6.65 – 6.68 (dd, 2H, 7.1 Hz, 1.2 Hz, H4,9), 7.02 –
7.08 (m, 2H, Ho), 7.10 – 7.20 (m, 1H, Hp), 7.9 (m, 2H, Hm),
7.34 (m, 2H, H5,8), 7.40 (dd, 2H, 8.3 Hz, 1.2 Hz, H6,7). –
1H NMR (399.8 MHz, CD2Cl2, 23 ◦C): δ = 6.32 (br. d, 2H,
NH, J(31PN1H) = 14.3 Hz), 6.70 (dd, 2H, 7.3 Hz, 0.8 Hz,
2
H
4,9), 7.04 (dm, 2H, 8.4 Hz, Ho), 7.17 (m, 1H, Hp), 7.26 –
7.30 (m, 2H, Hm), 7.32 (m, 2H, H5,8), 7.39 (dm, 2H, 8.1 Hz,
H
6,7). – EI-MS (70 eV) for C16H13N2OPSe (359.99): m/z
◦
6a: 1H NMR (250.1 MHz, CD2Cl2, 23 C): δ = 0.96 (d,
(%) = 360 (35) [M]+, 267 (11) [M–C6H5O]+, 203 (11),
187 (86) [M–C6H5O–Se]+, 186 (100) [M–C6H5OH–Se]+,
140 (9).
9 H, 3CH3, 3J(31P,1H) = 13.6 Hz), 5.06 (br. d, 2H, NH,
2J(31PN1H) = 38.0 Hz), 6.58 – 6.61 (m, 2H), 7.05 – 7.15 (m,
4H). – EI-MS (70 eV) for C14H17N2P (244.11): m/z (%) =
244 (5) [M]+, 205 (13), 187 (100) [M–(CH3)3C]+, 186 (48)
[M–(CH3)3CH]+.
Acknowledgement
7a: 1H NMR (250.1 MHz, CDCl3, 23 ◦C): δ = 5.50 (br. d,
2H, NH, 2J(31PN1H) = 36.9 Hz), 6.48 – 6.52 (m, 2H), 6.90 –
Support of this work by the Deutsche Forschungsgemein-
schaft is gratefully acknowledged.
[1] a) M. Alajarin, C. Lopez-Leonardo, P. Llamas-Lorente,
Top. Curr. Chem. 2005, 250, 77; b) P. J. Guiry, C. P.
Saunders, Adv. Synth. Catal. 2004, 346, 497; c) M. R. I.
Zubiri, J. D. Woollins, Comments Inorg. Chem. 2003,
24, 189; d) G. G. Briand, T. Chivers, M. Krahn, Co-
ord. Chem. Rev. 2002, 233 – 234, 237; e) J. Ansell,
M. Wills, Chem. Soc. Rev. 2002, 31, 259.
2005, 2097; g) X. Liu, P. Ilankumaran, I. A. Guzei, J. G.
Verkade, J. Org. Chem. 2000, 65, 701.
[3] a) T. Bauer, S. Schulz, M. Nieger, I. Krossing, Chem.
Eur. J. 2004, 10, 1729; b) B. Wrackmeyer, C. Ko¨hler,
W. Milius, J. M. Grevy, Z. Garcia-Hernandez, R. Con-
treras, Heteroat. Chem. 2002, 13, 667; c) J. Peralta-
Cruz, V. I. Bakhmutov, A. Ariza-Castolo, Magn. Re-
son. Chem. 2001, 39, 187; d) G. Hagele in Aminophos-
phonic and Aminophosphinic Acids: Chemistry and Bi-
ological Activity, (Eds.: V. P. Kukhar, H. R. Hudson),
Wiley, Chichester, 2000, pp. 217 – 284; e) B. Eich-
horn, H. No¨th, T. Seifert, Eur. J. Inorg. Chem. 1999,
2355; f) J. Burdon, J. C. Hotchkiss, W. B. Jennings,
Tetrahedron Lett. 1973, 4919; g) A. H. Cowley, J. R.
Schweiger, J. Am. Chem. Soc. 1973, 95, 4179; h) B. J.
Walker, J. Nelson, R. Spratt, J. Chem. Soc., Chem.
Commun. 1970, 1509; i) A. H. Cowley, M. J. S. Dewar,
W. R. Jackson, Jr., W. B. Jennings, J. Am. Chem. Soc.
1970, 92, 5206.
[2] a) K. Gholivand, Z. Shariatinia, S. M. Mashhadi,
F. Daeepour, N. Farshidnasab, H. R. Mahzouni,
N. Taheri, S. Amiri, S. Ansar, Polyhedron 2009, 28,
ˇ
ˇ
307; b) R. Sebesta, A. Skvorcova´, J. Organomet.
Chem. 2009, 694, 1898; c) S. Burck, D. Gudat,
M. Nieger, J. Tirree´, Dalton Trans. 2007, 1891;
d) M. S. Balakrishna, J. T. Mague, Organometallics
2007, 26, 4677; e) L. Eberhardt, D. Armspach, D. Matt,
L. Toupet, B. Oswald, Eur. J. Org. Chem. 2007,
5395; f) V. N. Tsarev, S. E. Lyubimov, O. G. Bon-
darev, A. A. Korlyukov, M. Yu. Antipin, P. V. Petro-
vskii, V. A. Davankov, A. A. Shiryaev, E. B. Benetsky,
P. A. Vologzhanin, K. N. Gavrilov, Eur. J. Org. Chem.
[4] a) A.-S. Chauvin, G. Bernardinelli, A. Alexakis, Tetra-
- 10.1515/znb-2009-11-1222
Downloaded from De Gruyter Online at 09/12/2016 12:36:48AM
via free access

B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
1411
hedron: Asymmetry 2006, 17, 2203; b) S. Reymond,
J. M. Brunel, G. Buono, Tetrahedron: Asymmetry 2000,
11, 1273; c) S. E. Denmark, P. C. Miller, S. R. Wilson,
J. Am. Chem. Soc. 1991, 113, 1468; d) J. M. A. Al-
Rawi, M. A. Sheat, N. Ayed, Organic Magnetic Reso-
nance 1984, 22, 336; e) J. P. Gouesnard, J. Dorie, G. J.
Martin, Can. J. Chem. 1980, 58, 1295; f) J. H. Har-
gis, S. D. Worley, W. B. Jennings, M. S. Tolley, J. Am.
Chem. Soc. 1977, 99, 8090; g) R. O. Hutchins, B. E.
Maryanoff, J. P. Albrand, A. Cogne, D. Gagnaire, J. B.
Robert, J. Am. Chem. Soc. 1972, 94, 9151.
[9] a) Z. Zala´n, H. Kivela¨, L. La´za´r, F. Fu¨lo¨p, K. Pihlaja,
Eur. J. Org. Chem. 2006, 2145; b) P. V. G. Reddy, C. S.
Reddy, C. N. Raju, Chem. Pharm. Bull. 2003, 51, 860;
c) H. Tye, C. Eldred, M. Wills, Tetrahedron Lett. 2001,
43, 155; d) P. V. G. Reddy, Y. H. Babu, C. S. Reddy,
D. Srinivasulu, Heteroat. Chem. 2002, 13, 340; e) S. L.
Deng, D. Z. Liu, Synthesis 2001, 2445.
[10] a) A. I. Zavalishina, N. N. Nurkulov, E. I.
Orzhekovskaya, A. R. Bekker, L. K. Vasyanina,
I. V. Bespalova, E. E. Nifant’ev, Zh. Obshch. Khim.
1995, 65, 777; b) S. A. Katz, V. S. Allured, A. D.
Norman, Inorg. Chem. 1994, 33, 1762; c) E. G. Bent,
R. Schaeffer, R. C. Haltiwanger, A. D. Norman, Inorg.
Chem. 1990, 29, 2608; d) J. P. Dutasta, P. Simon,
Tetrahedron Lett. 1987, 28, 3577; e) E. E. Nifant’ev,
A. I. Zavalishina, V. V. Kurochkin, E. I. Smirnova,
A. A. Borisenko, Zh. Obshch. Khim. 1985, 55,
2031.
[5] a) M. L. Helm, S. A. Katz, T. W. Imiolczyk, R. M.
Hands, A. D. Norman, Inorg. Chem. 1999, 38, 3167;
b) P. Delangle, J.-P. Dutasta, J.-P. Declercq, B. Tinant,
Chem. Eur. J. 1998, 4, 100; c) S. A. Bourne, X. Y.
Mbianda, T. A. Modro, L. R. Nassimbeni, H. Wan, J.
Chem. Soc., Perkin Trans. 2 1998, 83; d) A. De la Cruz,
K. J. Koeller, N. P. Rath, C. D. Spilling, I. C. F. Vas-
concelos, Tetrahedron 1998, 54, 10513; e) W. G. Ben-
trude, R. O. Day, J. M. Holmes, G. S. Quin, W. N. Set-
zer, A. E. Sopchik, R. R. Holmes, J. Am. Chem. Soc.
1984, 106, 106.
[11] a) G. R. Knox, Proc. Chem. Soc. London 1959, 56;
b) G. R. Knox, P. L. Pauson, J. Chem. Soc. 1961, 4615;
c) A. N. Nesmeyanov, V. N. Drozd, V. A. Sazonova,
Dokl. Akad. Nauk SSSR 1963, 150, 321.
[6] a) S. E. Denmark, X. Su, Y. Nishigaichi, D. M. Coe,
K.-T. Wong, S. B. D. Winter, J. Y. Choi, J. Org. Chem.
1999, 64, 1958; b) E. E. Nifant’ev, A. I. Zavalishina,
E. I. Orzhekovskaya, A. R. Bekker, I. A. Skumbrii, T. V.
Makarkina, Zh. Obshch. Khim. 1989, 59, 2497; c) V. V.
Kurochkin, A. I. Zavalishina, E. I. Orzhekovskaya,
A. R. Bekker, A. G. Agranovich, E. E. Nifant’ev, Zh.
Obshch. Khim. 1987, 57, 311; d) E. I. Smirnova, A. I.
Zavalishina, A. A. Borisenko, M. N. Rybina, E. E. Ni-
fant’ev, Zh. Obshch. Khim. 1981, 51, 1956.
[7] a) P. Bhattacharyya, A. M. Z. Slawin, J. D. Woollins,
J. Organomet. Chem. 2001, 623, 116; b) Y. Ozoe,
K.-I. Niina, K.-I. Matsumoto, I. Ikeda, K. Mochida,
C. Ogawa, A. Matsuno, M. Miki, K. Yanagi, Bioorg.
Med. Chem. 1998, 6, 73; c) E. E. Nifant’ev, A. I.
Zavalishina, V. G. Baranov, E. I. Orzhekovskaya, L. K.
Vasyanina, M. Yu. Antipin, B. K. Sadybakasov, Yu. T.
Struchkov, Zh. Obshch. Khim. 1993, 63, 1748; d) A. E.
Nifant’ev, A. I. Zavalishina, N. N. Nurkulov, E. I.
Orzhekovskaya, A. R. Bekker, N. S. Magomedova,
V. K. Bel’skii, Zh. Obshch. Khim. 1993, 63, 1739.
[8] a) K. Gholivand, M. Pourayoubi, Z. Shariatinia, Poly-
hedron 2007, 26, 837; b) K. Gholivand, Z. Sharia-
tinia, H. R. Mahzouni, S. Amiri, Struct. Chem. 2007,
18, 653; c) E. E. Nifant’ev, A. I. Zavalishina, E. I.
Orzhekovskaya, N. M. Selezneva, L. K. Vasyanina,
E. V. Vorontsov, A. I. Stash, V. K. Bel’skii, Russ.
J. Gen. Chem. 2002, 72, 193; d) E. E. Nifantiev,
A. I. Zavalishina, E. I. Orzhekovskaya, N. N. Nurkulov,
L. K. Vasyanina, A. R. Bekker, V. K. Belskii, A. I.
Stash, Phosphorus, Sulfur, Silicon Relat. Elem. 1997,
123, 89.
[12] A. Shafir, M. P. Power, G. D. Whitener, J. Arnold,
Organometallics 2000, 19, 3978.
[13] B. Wrackmeyer, E. V. Klimkina, W. Milius, Inorg.
Chem. Commun. 2004, 7, 884.
[14] K. Pilgram, F. Korte, Tetrahedron 1963, 19, 137.
[15] a) M. P. Simonnin, R. M. Lequan, F. W. Wehrli, J.
Chem. Soc., Chem. Commun. 1972, 1204; b) K. Bar-
los, H. No¨th, B. Wrackmeyer, W. McFarlane, J. Chem.
Soc., Dalton Trans. 1979, 801.
[16] A. Bax, R. Freeman, J. Magn. Reson. 1981, 45, 177.
[17] W. McFarlane, B. Wrackmeyer, Inorg. Nucl. Chem.
Lett. 1975, 11, 719.
[18] W. McFarlane, B. Wrackmeyer, J. Chem. Soc., Dalton
Trans. 1976, 2351.
[19] T. Parella, J. Magn. Reson. 2004, 167, 266.
[20] H. Duddeck, Prog. Nucl. Magn. Reson. Spectrosc.
1995, 27, 1.
[21] C. J. Jameson, Isotopes in the Physical and Biomedical
Sciences, Vol. 2 (Eds.: E. Buncel, J. R. Jones), Elsevier,
Amsterdam 1991, pp. 1 – 54.
[22] E. Kupcˇe, B. Wrackmeyer, J. Magn. Reson. 1992, 97,
568.
[23] a) E. Kupcˇe, B. Wrackmeyer, Magn. Reson. Chem.
1991, 29, 351; b) B. Wrackmeyer, E. Kupcˇe,
A. Schmidpeter, Magn. Reson. Chem 1991, 29, 1045;
c) B. Wrackmeyer, E. Kupcˇe, G. Kehr, J. Schiller,
Magn. Reson. Chem. 1992, 30, 304; d) B. Wrackmeyer,
C. Ko¨hler, E. Kupcˇe, Magn. Reson. Chem. 1993, 31,
769; e) B. Wrackmeyer, C. Ko¨hler, Magn. Reson.
Chem. 1993, 31, 573; f) B. Wrackmeyer, E. Garcia-
Baez, F. J. Zuno-Cruz, G. Sanchez-Cabrera, M. J. Ros-
ales, Z. Naturforsch. 2000, 55b, 185.
- 10.1515/znb-2009-11-1222
Downloaded from De Gruyter Online at 09/12/2016 12:36:48AM
via free access

1412
B. Wrackmeyer et al. · 1,3,2-Diazaphospha-[3]ferrocenophanes
[24] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuse-
ria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery,
Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Mil-
lam, S. S. Iyengar, J. Tomasi, V. Barone, B. Men-
nucci, M. Cossi, G. Scalmani, N. Rega, G. A. Pe-
tersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toy-
ota, R. Fukuda, J. Hasegawa, M. Ishida, T. Naka-
jima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li,
J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo,
J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski,
P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador,
J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D.
Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D.
Rabuck, K. Raghavachari, J. B. Foresman, J. V. Or-
tiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski,
B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,
I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A.
Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challa-
combe, P. M. W. Gill, B. Johnson, W. Chen, M. W.
Wong, C. Gonzalez, J. A. Pople, GAUSSIAN 03 (revi-
sion B.02), Gaussian, Inc., Pittsburgh PA (USA) 2003.
[25] B. Wrackmeyer, E. V. Klimkina, H. E. Maisel, O. L.
Tok, M. Herberhold, Magn. Reson. Chem. 2008, 46,
530.
[26] K. Stott, J. Keeler, Q. N. Van, A. J. Shaka, J. Magn. Re-
son. 1997, 125, 302.
[27] a) G. A. Morris, R. Freeman, J. Am. Chem. Soc. 1979,
101, 760; b) G. A. Morris, J. Am. Chem. Soc. 1980,
102, 428; c) J. Schraml in The Chemistry of Or-
ganic Silicon Compounds, Vol. 3 (Eds.: Z. Rappoport,
Y. Apeloig), Wiley, Chichester, 2001, pp. 223 – 339.
[28] M. Herberhold, Angew. Chem. 1995, 107, 1985;
Angew. Chem., Int. Ed. Engl. 1995, 34, 1837.
[29] CCDC 739348 (4a at 293 K), CCDC 739349 (4b
at 293 K) and CCDC 739350 (6d at 293 K) con-
tain the supplementary crystallographic data for this
paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data request/cif.
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