1,3-Distanna-2-phospha-[3]ferrocenophanes. Synthesis, reactivity and NMR spectroscopic properties

Article abstract of DOI:10.1515/znb-1999-0113

1,1,3,3-Tetramethyl-2-organo(R)-1,3-distanna-2-phospha-[3]ferrocenophanes [R = Me (2a), ^tBu (2b), C₆H₁₁ (2c), Ph (2d)] and one arsa-analogue 2d(As) were obtained from the reaction of 1,1′-bis(chlorodimethylstannyl)ferrocen

Full text of DOI:10.1515/znb-1999-0113

l,3-Distanna-2-phospha-[3]ferrocenophanes - Synthesis, Reactivity and
NMR Spectroscopic Properties
Max Herberhold*, Udo Steffl, Bernd Wrackmeyer*
Laboratorium für Anorganische Chemie, Universität Bayreuth, D-95440 Bayreuth, Germany
Herrn Prof. Dr. Dr. h.c. mult. Hans Bock zum 70. Geburtstag gewidmet
Z. Naturforsch. 54 b, 57-62 (1999); received July 28, 1998
Ferrocene, Tin, Phosphorus, NMR Data, Coupling Signs
l,l,3,3-Tetramethyl-2-organo(R)-l,3-distanna-2-phospha-[3]ferrocenophanes [R = Me (2a),
rBu (2b), CöHii (2c), Ph (2d)] and one arsa-analogue 2d(As) were obtained from the reaction of
l,l'-bis(chlorodimethylstannyl)ferrocene 1 with either bis(trimethylsilyl)methylphosphane or
the dilithio derivatives, Li2PR and Li^AsPh, respectively. All compounds 2 react with chalco-
gens (oxygen, sulfur, selenium) by cleavage of the Sn-P bonds and formation of the known
l,3-distanna-2-chalcogena-[3]ferrocenophanes. In contrast, 2d traps pentacarbonylmetal frag-
ments [M(CO)5] to give the stable phosphane complexes [M = Cr (4d), Mo (5d), W (6d)].
The l,l'-bis(diorganophosphanostannyl)ferrocenes [R = fBu (3b), Ph (3d)] were prepared for
comparison of NMR data. The ferrocenophanes 2 are fluxional with respect to fast movement
of the cyclopentadienyl rings which induces inversion at the pyramidal phosphorus atom. This
dynamic process is slow in the cases of 2d(As) and of the pentacarbonyl complexes 4d - 6d.
All new compounds were characterised by 'H, i3C, 31P and 1l9Sn NMR spectroscopy. Various
2D heteronuclear shift correlations {e.g. 11P/1H and ll9Sn/'H) were carried out for the com-
pounds 2 and also for non-cyclic derivatives such as bis(trimethylstannyl)phenvlphosphane and
-arsane in order to determine absolute signs of coupling constants [e.g. 7(n Sn,’'P) > 0 and
2J(]l9Sn,' l7Sn) < 0]. The NMR data suggest that the molecular frameworks of the ferroceno-
phanes 2 are not particularly strained.
1. Introduction
scribe the synthesis and reactivity of the first 1,3-
distanna-2-phospha-[3]ferrocenophanes and of
a
l,3-distanna-2-arsa-[3]ferrocenophane. In addition
to their promising ligand properties, the phospho-
rus compounds, in particular, are o f interest with
respect to their NM R spectroscopic features con-
sidering the presence of several magnetically active
nuclei such as *H, 13C, 3IP, 117Sn and 119Sn.
Ferrocenophanes [1] containing tin atoms in
the bridge are o f considerable interest owing to
both the reactivity o f tin-element bonds and the
stabilising effect of the rather rigid and bulky
1,l'-ferrocenediyl group. Thus, l-stanna-[l]ferro-
cenophane undergoes ring-opening polymerisation
[2, 3], and, as
a result o f the strained struc-
2. Results and Discussion
ture, transition metal fragments insert into one
o f the Sn-C (l) bonds [3], l,2-Distanna-[2]ferro-
cenophane [4] reacts with Pt(0) fragments by
oxidative addition to give l,3-distanna-2-platina-
[3]ferrocenophanes [5, 6], which can be regarded
as model compounds for the catalytic distanna-
tion of alkynes [7, 8]. Chalcogens readily in-
sert into the Sn-Sn bonds o f both 1,2-distanna-
[2]ferrocenophane [9] and l,2,3-tristanna-[3]ferro-
cenophane [10]. In the present report we now de-
2.1. Synthesis and reactivity o f 1,3-distanna-2 -
phospha-[3Jferrocenophanes
The synthetic approach is outlined in Scheme
1 which also reveals information on the reactiv-
ity of l,3-distanna-2-phospha-[3]ferrocenophanes.
l,l'-Bis(chlorodimethylstannyl)ferrocene 1 [11,12]
appears to be a most convenient starting mate-
rial for the synthesis of various ferrocenophanes
containing at least two tin atoms attached to the
ferrocene unit [4, 9], The salt elimination reac-
tion of 1 with various dilithiophosphanes affords
the compounds 2b - d in moderate to good yields.
* Reprint requests to Prof. Dr. M. Herberhold
or Prof. Dr. B. Wrackmeyer.
0932-0776/99/0100-0057 $ 06.00 © 1999 Verlag der Zeitschrift für Naturforschung, Tübingen • www.znaturforsch.com
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M. Herberhold et al. ■1,3-Distanna-2-phospha-[3]ferrocenophanes
58
SnMe2_PR2
—SnMe2CI
ü
“
+
2 LiPR;
Fe
1
SnMe2-PR2
SnMe2CI
3 b
d
+ (Me3Si)2PMe (a)
+ Li2PR(b,c,d)
R = tßu Ph
-Sn
\± J
\
Fe
A
V W /- sM/e2^t- r
M(CO)5
2 a
b
c d
Scheme 2.
R = Me tßu Cy Ph
< Q r «C
substituent R occupies the exo-position. Since the
dynamic processes in 2 lead to averaged resonance
signals of the SnMe groups and of the ferrocenediyl
units [‘H (2,5)/13C(2,5) and ‘H (3,4)/I3C(3,4)], the
lone pair of electrons at the phosphorus atom and
7 8 9
4d 5d 6d
M= Cr Mo W
E = O S Se
Scheme l.
The arsenic derivative 2d(As) was prepared in the
same way, using dilithio(phenyl)arsane. An alter-
native route is available via the reaction of 1 with
bis(trimethylsilyl)methylphosphane which leads to
2a by cleavage o f the P-Si bonds and elimination
of two equivalents of Me^SiCl. The reactions of 1
with two equivalents of lithio(diorgano)phosphanes
afford the open stannylphosphanes 3b,d which were
studied by NM R spectroscopy in order to provide a
meaningful comparison of NM R data.
the group R must on average occupy identical po-
sitions (Scheme 2; rapid interconversion of A and
B). This can be explained either by fast inversion at
the pyramidal phosphorus atom (which is unlikely
because of the rather high activation energy of this
process) or by movement o f the two cyclopentadi-
enyl rings against each other (Scheme 2: C). The
latter dynamic process has been proposed in order
to explain the dynamic behaviour of 1,2,3-trichalco-
gena-[3]ferrocenophanes [14]. In the case of the
pentacarbonylmetal com plexes 4d - 6d, all dynamic
processes are slow at room temperature, as shown
by the characteristic patterns of signals in the 'H
and l3C NM R spectra.
Addition of pentacarbonylmetal fragments
[M(CO)5] (M = Cr, Mo, W) in THF to 2d leads
to the respective phosphane com plexes as shown
in the cases of 4d - 6d which are analogous to
known com plexes in which bis(trimethylstannyl)-
phenylphosphane serves as a ligand [13]. In con-
trast, all compounds 2 react with chalcogens E = O,
S, Se by cleavage of the Sn-P bonds (Sn-As bonds
in the case of 2d(As)) to give the known [9, 10]
1,3-distanna-2-chalcogena-[3]ferrocenophanes and
the phosphorus(V) chalcogenides [RP(E)E]n.
The typical magnitude [15] of the coupling con-
stants 'y(119Sn,3lP), observed both in the 31P and
1l9Sn NMR spectra, indicates the presence of Sn-P
bonds. It is important to know the sign of coup-
ling constants 7(3IP,X) in order to use this param-
eter as a diagnostic criterion. Changes in the mag-
nitude of l'y(ll9Sn,3lP)l in going from the phos-
phane 2d to the pentacarbonylmetal com plexes 4d
- 6d have been observed previously for compara-
ble phosphane complexes [13, 16], and there was
no change in the sign of this coupling constant. We
have confirmed this trend in the case of the ferro-
cenophanes 2 by determining the absolute positive
sign of ’y(119Sn,31P), as expected [13] (the sign of
the reduced coupling constant1K (119Sn,3lP) is neg-
ative because of 7 ( ll9Sn) < 0). The negative sign
of 'K (119Sn,3lP) can be traced to negative contri-
butions to the Fermi contact term arising from the
presence of the lone pair o f electrons at the phos-
2.2. NMR spectroscopic results
All NM R spectroscopic data (Tables I - III) are
in support of the proposed structures of the new
compounds 2 - 6. The 1H and l3C NM R spectra of
the ferrocenophanes 2 indicate fluxional structures,
in contrast to the situation in the com plexes 4 - 6 .
Low temperature 'H and l3C NMR spectra of 2d
prove the presence of a rigid structure (_\G #(Coai.) =
67.7 ± 2 kJ/mol at -10°C). In the case of 2d(As), the
dynamic processes are already slow at ambient tem-
perature. For steric reasons, it is assumed that the
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M. Herberhold et al. ■l,3-Distanna-2-phospha-[3]ferrocenophanes
59
Table 1.1
H, l3C, 3'P a n d 119Sn NMR data|a| of the 1,3-distanna-2-phospha-[3] ferrocenophanes 2a - d and of the 2-arsa
analogue 2d(As).
<$I3C
C(l)
<$"9Sn
-47.6
(736.0) [362.3]
(736.0)
No.
(5'H
H(2,5)
631P
C(3,4)
70.2
H(3,4)
4.21
PR
PR
C(2,5)
74.3
SnMei
SnMe2
-8.9
2a
4.01
4.05
4.08
4.02
0.36
[50.3]
(1-3)
1.34
[56.2]
(5.4)
71.5
[n.m.]
« D
- 1.8
-211.3
[50.1] [39.6] [310 81 [19.5]
(-31.7)
[8.8]1 r
(5.8)
-4.9
2b
2c
4.21
4.22
4.21
4.23
1.33
[4.1]
(12.3)
70.0
[n.m.]
(< 1)
74.5
[49.6]
70.7
[38.4]
31.6, 36.6
- 111.8
-5.3
0.49
[51.3]
( 1. 1)
(793.0) [362.6]
(793.0)
[302.31 [18.5], [25.6]
[8.7] |b1 (28.9), (12.1)
(6 .2)
-155.2
1.4
0.45
2.3 [cl
70.5
[n.m.]
« D
74.8
70.9
-8.7
31.0,38.5 [dl
[50.2] [38.4] [305.6} [16.8], [38.5] (771.0) [367.7]
[8.5] |b1 (26.6), ( 11.8)
( 10.2)
(771.0)
2d
[e]
7.0-7.7
7.0-7.8
74.6
70.7
-7.0
132.5 [fl
[15.4]
(23.9)
-156.1
1.3
0.38
[51.0]
(1.9)
71.0
[435.6]
(735.0) [365.4]
(735.0)
[50.8] [39.8] [320.71
[9.0] [b1
(9.2)
-6.70
-
2d(As) 4.02
74.7
[54.2]
74.7
70.7
[39.9] [294.6]
70.4
134.8 lgl
[n.m.]
-14.5
[393.7]
0.48
[52.8]
0.49
72.3
[416.7]
[1-8]
4.11
-6.73
[52.8]
[53.8]
[294.0]
[40.6]
13/
^3 I d 13/
/ 3 l r , l '
[a| In CöDft at room temperature; coupling constants / ( 'l9Sn,' H), / ( ll9Sn,IJC) in brackets, 7(JIP,'H), J (''P ,'’C),
yC'^Sn 'P) in parentheses;|b| 3/( Sn,P,Sn,l3C );[cl <5'H (cyclohexyl H(2-6): 1.9, 1.5, 1.1 multiplets without assign-
ment; {d] <5l1C(3/5) (cyclohexyl) = 27.7 (9.5), 6l3C(4) = 26.0;[e| at -20 °C in [Dx]toluene: b' H = 4.05,4.02 (H2/5), 4.21
(broad; H3/4), 0.36 [51.2] (2.4), 0.34 [51.0] (1.4) (SnMe.); <513C (-40 °C) = 74.6 (broad; C(2/5), 70.9, 70.6 (C3/4),
-6.8 (7.1), -6.9 (10.6) (SnMe?); m bn C(ortho) = 135.6 [30.7] (14.4), 6]yC(meta) = 128.6 [2.4] (5.3), <5I3C(para) =
126.7 [6.5];lgl buC(ortho) = 136.5 [26.4], b"C(meta) = 129.6, 8]?C(para) = 126.9.
ble to determine the negative sign of ]y(3lP,13C),
the positive sign of 27(3lP,1HMe) and the nega-
tive sign of 3J (ll9Sn,P,C,'H) in 2a. Noteworthy
in this context is the determination of the neg-
ative sign of 2J(l19Sn,' 17Sn) in 2a, since only
few examples of signs of geminal Sn-Sn cou-
plings are known [21, 24]. We have also de-
termined the negative sign of 2y ('l9S n ,'l7Sn) in
bis(trimethylstannyl)phenylphosphane and -arsane,
(M e3Sn)2PPh and (M e^Sn^AsPh, for comparison.
This was achieved by a 2D 119Sn/'H HETCOR ex-
periment, based on long range coupling constants
phorus atom [17]. In the com plexes 4d - 6d this lone
pair of electrons is engaged in the coordinative P-M
bond, and therefore, negative contributions should
be reduced in a similar way as it was found for
other stannylphosphane metal com plexes [13, 16]
or stannylphosphane borane com plexes [18]. The
signs of other coupling constants involving 31P are
even more difficult to predict and therefore experi-
mental evidence is required.
The determinations o f coupling signs are based
either on appropriate ID heteronuclear double ex-
periments [13, 19] or on 2D heteronuclear shift cor-
relations (HETCOR) relating two active nuclei (e.g.
3IP and 'H) and one passive nucleus (e.g. ll9Sn
or ll7Sn) [18, 20, 21], These experiments (exam-
ples are given in the Figs. 1 and 2) lead to the
determination of absolute signs of coupling con-
stants, once a so-called “key coupling constant”
is involved for which the absolute sign is known
[e.g. 17 (13C ,1H) [22] or 2J(U9Sn,]HMe) [23]]. On
the basis of such experiments it proved possi-
4y(119Sn,P,Sn,C,'H) and 47 ('19Sn,As,Sn,C,’H) «
Hz, which enables one to compare the signs of
2K('^Sn/HsnM e) and 2K (!19S n ,'l7Sn), as has been
described previously [2 1 ].
1
The chemical shifts of heavy nuclei such a s 31P or
119Sn and also the coupling constants in which these
nuclei are involved should indicate the influence
of the ferrrocenophane structure when compared
with data for non-cyclic derivatives. The chem i-
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60
M. Herberhold et al. ■1,3-Distanna- 2-phospha-
[3]ferrocenophanes
P and 119Sn NMR data|a| of the pentacarbonylmetal phosphane complexes 4d
Table II. 'H, l3C, 31
- 6d.
<5'H
H(2,3,4,5)[bl
No
«^C
C(l)
<53iP
<5ll9Sn
11.1
PR
C(3,4)
C(2,5)
PR
SnMei
SnMe2
74.7
71.4
[42.8]
136.5 [c!
[ 10. 1]
(4.1)
4d 4.25 (2 H)
4.26 (4 H)
0.61
6.7-7.6 70.0
[420.3]
-5.5
-110.3
(235.5) [92.8]
(235.5)
[9.3][dI
[52.0]
(3.1)
0.51
[54.6]
(0.9)
74.5
[331.6]
(7.9)
-6.4
3.83 (2 H),
(2.6)
71.1
[55.5]
[43.4]
[333.9] [6.9][dl
( 12.0 )
-4.3
[53.3]
(2.1)
0.78
5d 4.14(2 H)
4.15 (2 H)
6.7-7.6 71.7
74.7
71.3
134.6 |el
[8.5]
(8.0 )
-130.3
(203.0) [136.2]
(203.0)
11.6
[441.2]
(< D
[316.4] [11. 1] ldl
(7.4)
-5.7
[53.5]
(2.5)
0.60
[53.8]
[42.8]
70.6
[43.0]
4.08 (2 H)
4.04 (2 H)
[52.9]
(2 .2)
0.83
[53.6]
(2.5)
0.62
[319.0] [11.0] ldl
( 11. 1)
-4.1
[317.6] [ 11.1] ld] [8.3]
(7.6) (7.9)
6d 4.23 (2 H)
4.24 (2H)
6.9-7.5 71.4
74.7
[437.3] [54.8]
71.1
[42.2]
70.9
134.7 [f] -152.9
13.4
(150.5) [108.0]
4.25 (2 H)
3.92 (2 H)
[74.5
[55.4]
(150.5)
«
1)
[g]
[41.6] -5.5
[320.4]
[53.0]
(2.3)
[11.1] [d]
(6.8)
[a) In CftDö at room temperature; coupling constants ./('19Sn,'H), •/('l9Sn,13C) in brackets, /( 3iP,'H), 7(3IP,I3C),
•/(' l9Sn,_1P) in parentheses;[b| without assignment;[c] b^C(ortho) = 133.5 [22.31 (7.6), 6l?lC(meta) = 129.0 [2.5] (7.9),
6"C(para) = 128.6 [2.2]; <5I3C (CO) 217.9 [10.6] (8.8), 221.3 [3.51 (6.7);[dl 3/ ( 'r9Sn,P,Sn,l3C );[el 6n C{ortho) = 133.9
[20.4] (12.1), <§13C(meta) = 129.0 (7.6), b^Cipara) = 127.21: <$,3C (CO) 206.5 (6.2), 211.6 (13.2), 217.2 (10.5); [f]
b"C(ortho) = 133.9 [20.21(8.7), b^C(meta) = 129.0 (8.5), b^Cipara) = 127.4; <513C (CO) 198.2 (4.2), 204.9 (11.1),
206.8 [4.1] (12.5);[g] l7(10W,3,P) = 198.2 Hz.
Table III. 'H, 13C, 3,P and ll9Sn NMR datala] of the 1,1 '-bis(phosphanyldimethylstannyl)ferrocenes 3b,d.
<S'H
H(2,5) H(3,4)
<$3IP
<5ll9Sn
-47.6
No
613C
C(l)
C(3,4)
C(2,5)
74.9
p r 2
p r 2
SnMe2
-8.2
SnMe2
3b 4.05
4.21
0.48
1.32
69.0
70.8
32.5, 36.4
-57.8
[702.0] (702.0)
[51.3]
(2.0)
0.39
[53.7]
(1.6)
[4.3]
( 12.0)
7.0-7.6 69.1
[485.2]
(9.6)
[476.8] [50.1]
(9.2)
[39.8]
[304.6] [18.0], [25.8]
(5.8)
-8.4
[312.2]
(6.5)
(28.9), (12.5)
137.5 C (l)[bf
[18.2]
-54.1
-12.7
3d
4.01
4.19
74.3
[50.5]
71.1
[38.8]
[614.0] (614.0)
(25.5)
[aI In C5D6 at room temperature; coupling constants ./('l9Sn,'H). 7(ll9Sn,l3C) in brackets 7(3iP,'H), 7(3iP,i3C),
7(ll9Sn, P) in parentheses;[b] b"C{ortho) = 135.7 ]25.5] (12.0); bn C(meta) = 128.6 (5.0); <Sl3C {para) = 126.7.
that there is no particular strain in the structures
of the ferrocenophanes 2 and 4d - 6d, and that the
bond angles at the phosphorus atoms are compara-
ble to those of non-cyclic compounds. This is also
supported by the NM R data (Table III) of the fer-
rocene derivatives 3b, d.
cal shifts <531P = -329.6 and <5119Sn = +14.2 and
the coupling constants ^ ('^ S n ,31?) = +724.0 Hz
and 2/ ( ll9Sn,119Sn) = -313.8 for (M e3Sn)2PPh and
(M e3Sn)2PPh-M (CO)5 (M = Cr, W ) [13, 25] are
very similar to the data obtained here for 2d. This
is also true for <5119Sn = -1.7 and 2/ ( 119Sn,ll9Sn) =
-396.0 observed for (M ejSn^A sPh and 2d(As). In
the cases of '7(119Sn,31P) and 2y (119Sn,ll7Sn), we
have confirmed that the sign of the coupling con-
stants is the same in the ferrocenophanes and in their
non-cyclic counterparts. Therefore, it is concluded
Experimental
All necessary precautions were taken to exclude oxy-
gen and moisture during the synthesis and handling of
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M. Herberhold et al. • l,3-Distanna-2-phospha-[3]ferrocenophanes
61
'j( H9Sn.3lP)
2K ("9Sn,ll7Sn) < 0
'K ("9Sn,3lP )< 0
*
2J(n9Sn,"7Sn) = - 362.3 Hz
♦
'j( " 9Sn,3,P) = +735.7 Hz
*
*
*
*
J
_________________________ 0 _
Fig. 2. Contour plot of the 92.1 MHz 1l9Sn/'H heteronu-
clear shift correlation of 2a based on 3/ ( ’19Sn,P,C,' H).The
negative tilt of the cross peaks for tin satellites indicates
that the signs of 3K(Sn,P,C.‘H) (>0) and 2K(Sn,Sn) (< 0)
[27(Sn,Sn) also < 0] are opposite.
Fig. 1. Contour plot of the 101.7 MHz 2D 3iP/'H het-
eronuclear shift correlation based on 2/( 31P,1HMe) for 2a.
The negative tilt of the cross peaks for tin satellites indi-
cates that the signs o f 17(Sn,31P) (> 0) and 37(1l9SnP,C,1H)
(< 0) are opposite.
/ ,1,2,3,3-Pentamethyl-l,3-distanna-2-phospha-[3Jferro-
cenophane (2a)
the compounds. Starting materials such as Fe(CsH4-
SnMe2Cl)2 1 [12], MeP(SiMe3)2[26], Li2PR, LiPR2 [27]
and Li2AsPh [28], PhPH2 [29], and analogously fBuPH2,
CöHi iPH2, PhAsH2 [30] were prepared as described. The
phosphanes fBu2PH and Ph2PH and 1.6 M solutions of
"BuLi in hexane were used as commercial samples.
NMR spectra were recorded on Bruker ARX 250, AC
300 or DRX 500 spectrometers, equipped with multinu-
clear units and accessories for measurements at variable
temperatures. Chemical shifts are given with respect to
Me4Si [61H (CHCI3/CDCI3) = 7.24, (C6D5CD2H) = 2.03;
<513C (CDCI3) = 77.0, (C6D5CD3) = 20.4], H3PO4, 85%
aq. for <S3IP = 0, and Me4Sn [<5,l9Sn = 0 with X(119Sn) =
37.290665 MHz], The assignment of ‘H and l3C NMR
signals was based on the presence ll7,/ll9Sn satellites, to-
gether with routinely performed 2D 1H /1H COSY and
2D i3C/'H HETCOR experiments. All conditions for 2D
HETCOR experiments were optimised by appropriate 1D
polarisation transfer experiments [31 ]. IR Spectra: Perkin
Elmer 983 G spectrometer; El MS spectra (70 eV): Finni-
gan MAT 8500 spectrometer with direct inlet (the calcu-
lated isotope distributions were found to be in agreement
with the experimental patterns).
A solution of 1 (0.1 g; 0.18 mmol) in toluene (10 ml)
is prepared and MeP(SiMe3)2 (0.04 g; 0.18 mmol) is in-
jected. The mixture is stirred for 2 h at room temperature
and then the solvent is removed in vacuo. The remain-
ing orange oil is identified ('H , 31P NMR) as pure 2a;
C 15H23FePSn2, El MS: m/e (%) = 528 (60) [M+], 365
(100) [M+ - SnMe3].
1,1,3,3-Tetramethyl-2-organo-1,3-distanna-2-phospha-
[3]ferrocenophanes (2b - d)
Generalprocedure: A solution of 1 (0.15 g; 0.27 mmol)
in THF (20 ml) is added to a freshly prepared suspension
of Li2PR in THF (15 ml) at 0 °C. The reaction mixture
is stirred at room temperature for 5 h, then the solvent is
removed in vacuo and the residue extracted with hexane.
After filtering off all insoluble material, the solvent is
again removed in vacuo, and the pure products ('H , 31P
NMR) are isolated as orange oils (69 -79 % yield). 2b:
Ci8H29FePSn2, El MS: m/e (%) = 570 (40) [M+], 334
(100) [Fe(C5H4)2SnMe2+]; 2c: C20H3iFePSn2, El MS:
m/e (%) = 596 (100) [M+]; 2d: C20H25FePSn2, El MS:
m/e (%) = 590 (100) [M+],
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M. Herberhold et al. • 1,3-Distanna-2-phospha-[3]ferrocenophanes
62
corresponding M(CO)6 in THF (20 ml) is stirred and
irradiated with UV light (Hanovia, 450 W) for 2 - 4 h. The
solvent is removed in vacuo, and the residue is dissolved
in CH2CI2. Addition of hexane leads to precipitation of
the complexes as yellow solids. 4d (yield 85 %; m.p. 176-
178 °C): C25H25G- FeO?PSn2, El MS: m/e(%) =782 (25)
[M+], 642 (100) [M+ - 5CO]; 5d (61 %; m.p. 177 °C):
C25H25FeMo0 5 PSn2, El MS: m/e(%) = 826 (10) [M+],
590 (100) [M+ - Mo(CO)5]; 6d (32 %; m.p. 186-189 °C):
C25H25Fe05PSn2W, El MS: m/e(%) = 914 (20) [M+], 590
(100) [M+ - W(CO)5],
2d(As) is obtained in the same way as an orange oil
(yield 70.5 %), using Li2AsPh. C2oH25AsFeSn2, El MS:
m/e (%) = 633 (60) [M+], 467 (100) [M+ - AsPh - Me],
1,1 '-Bis[dimethyl(diorganophosphanyljstannylJferro-
cenes (3b,d)
The same procedure as described for 2b - d was applied
for the synthesis of the ferrocene derivatives 3b.d using
LiPR2. The complexes 3b.d are obtained as orange oils
in 75 - 80 % yield. 3b: C3oH56FeP2Sn2, El MS: m/e (%)
= 772 (100) [M+]; 3d: C38H4oFeP2Sn2, El MS: m/e (%) =
852(100) [M+].
Acknowledgements
1,1,3,3- Tetramethyl-2 -pentacarbonylmetal(phenyl)-1,3-
distanna-2-phospha-[3]ferrocenophanes (4d, 5d, 6d)
Support of this work by the Deutsche Forschungsge-
meinschaft and the Fonds der Chemischen Industrie is
gratefully acknowledged.
General procedure: A solution containing both 2d
(0.15 g; 0.25 mmol) and the stoichiometric amount of the
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