Hydrostannylation of phosphaalkynes

Article abstract of DOI:10.1002/(SICI)1099-0682(199802)1998:2<227::AID-EJIC227>3.0.CO;2-T

The hydrostannylation of phosphaalkynes 8 with tin hydrides 1 depends on the stoichiometry employed: Thus, the 1,2-dihydro-1,3-diphosphetes 10 are isolated when an excess of phosphaalkyne 8 is used. On the other hand, an increase in the tin hydride concentration favors the formation of the phosphanes 11 and 12. Synthesis of the 1,2-dihydro-1,3-diphosphetes 14 and 16 was achieved by the use of diorganotin hydrides 13 or chloro(organo)tin hydrides 4, respectively. An isolated and characterized by-product of the latter reaction was the phosphorus-carbon-tin cage 17. Furthermore, the following reactions of the 1,2-dihydro-1,3-diphosphetes 10 were performed: isomerization reactions, complexation reactions with transition-metal complexes, and substitution of the hydrogen atom by iodine.

Full text of DOI:10.1002/(SICI)1099-0682(199802)1998:2<227::AID-EJIC227>3.0.CO;2-T

FULL PAPER
Organophosphorus Compounds, 125[᭛]
Hydrostannylation of PhosphaalkynesȠ
Marion Schmitz, Rudolf Göller, Uwe Bergsträßer, Stefan Leininger, and Manfred Regitz*
Fachbereich Chemie der Universität Kaiserslautern,
Erwin-Schrödinger-Strasse, D-67663 Kaiserslautern, Germany
Fax: (internat.) ϩ 49(0)631/205-3921
Received September 22, 1997
Keywords: Hydrostannylation / Phosphaalkynes / 1,2-Dihydro-1,3-diphosphetes / Homocubanes / Carbonyl complexes
The hydrostannylation of phosphaalkynes 8 with tin hydrides
1 depends on the stoichiometry employed: Thus, the 1,2-di-
hydrides 13 or chloro(organo)tin hydrides 4, respectively. An
isolated and characterized by-product of the latter reaction
hydro-1,3-diphosphetes 10 are isolated when an excess of was the phosphorus-carbon-tin cage 17. Furthermore, the
phosphaalkyne 8 is used. On the other hand, an increase in
the tin hydride concentration favors the formation of the
phosphanes 11 and 12. Synthesis of the 1,2-dihydro-1,3-di-
following reactions of the 1,2-dihydro-1,3-diphosphetes 10
were performed: isomerization reactions, complexation reac-
tions with transition-metal complexes, and substitution of the
phosphetes 14 and 16 was achieved by the use of diorganotin hydrogen atom by iodine.
Introduction
Addition reactions of organotin compounds to unsatu-
rated systems have been known for a long time[2]. Following
the hydrostannylation of alkenes which, as a consequence
of the mild reaction conditions and high selectivity, has
found wide-ranging applications, the first 1,2-addition of
triorganotin hydrides to acetylenes was achieved in
1959[3][4]. In comparison to the hydrostannylation reactions
of the corresponding olefins, the additions to CϪC triple-
bond systems proceed more readily. The vinyltin com-
pounds 2 are the primary products of these reactions which
then undergo, albeit somewhat delayed, addition of a se-
cond equivalent of the triorganotin hydride 1 to furnish the
ditin compounds 3. Modification of the organotin hydride
by the introduction of a halogen atom to give the dior-
gano(halo)tin hydrides 4[5] provides further new possibili-
ties for the synthesis of numerous mixed substituted or-
ganotin compounds 5[6]
.
We recently reported on hydrostannylation reactions in
the chemistry of low-coordinated phosphorus, namely the
selective 1,2-addition of organotin compounds to Becker-
type phosphaalkenes 6 to furnish the stannylphosphanes
2 weeks gave rise to the 2-stannyl-substituted 1,2-dihydro-
1,3-diphosphetes 10 in good yields. The reaction of tributyl-
tin hydride (1a) with 1-adamantylphosphaalkyne (8b) re-
quired heating at 60°C for 4 hours for completion.
7[7]
.
The central theme of the present work is the reactivity of
organotin hydrides and organo(halo)tin hydrides towards
kinetically stabilized λ3σ1-phosphaalkynes and the related
question of whether the primary products of the 1,2-ad-
dition of tin hydrides to the PϪC triple-bond system will
be sufficiently stable to permit their isolation.
The natures of the 1,2-dihydro-1,3-diphosphetes 10a؊f
were deduced from their analytical and spectroscopic data.
The valency vibrations at 2160Ϫ2340 cmϪ1 in the IR spec-
tra provided the first evidence for the presence of the PH
function. A doublet of doublets at δ ϭ 6.78Ϫ7.8 with 1JH,P
coupling constants of between 163 and 168 Hz was found
in the 1H-NMR spectra for these protons, which were orig-
inally bonded to the tin atoms. The splitting into a doublet
of doublets and the integration values of the signals clearly
demonstrate that compounds 10 are 1:2 adducts formed
from one equivalent of the tin hydride 1 and two equiva-
Reactions with Triorganotin Hydrides 1
Reactions of the tin hydrides 1 with an excess of the
phosphaalkynes 8a؊c in n-pentane at room temperature for
[᭛]
Part 124: Ref.[1]
.
Eur. J. Inorg. Chem. 1998, 227Ϫ235
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
1434Ϫ1948/98/0202Ϫ0227 $ 17.50ϩ.50/0
227

M. Schmitz, R. Göller, U. Bergsträßer, S. Leininger, M. Regitz
FULL PAPER
A more careful consideration of the structures of com-
pounds 10 reveals the presence of two centers of chirality:
In addition to the asymmetric carbon atom C2 the phos-
phorus atom P1 should be chiral and configurationally
stable . However, only one set of signals was observed in all
of the NMR spectra and therefore it must be assumed that
only one diastereomer is formed in each case. An exact as-
signment to one of the possible isomers is not possible on
the basis of the spectroscopic data.
An increase in the tin hydride concentration favors the
increased formation of the phosphanes 11 and 12. When
triphenyltin hydride (1b) was used in excess the phosphanes
11 were formed in yields exceeding 75%, while the isomeric
compounds 12 were only observed as by-products (yields: <
5%). In comparison to triphenyltin hydride (1b), the lower
hydrostannylation activity of tributyltin hydride (1a)[17] was
not sufficient to alter the reaction course decisively in the
direction of the phosphanes 11 and 12; accordingly, the re-
action mixtures contained appreciable amounts (60%) of
the dihydrodiphosphetes 10 and a separation of the individ-
ual components was not possible.
The 31P-NMR and 1H-NMR spectra are of particular
diagnostic value for the structural elucidation of the distan-
nyl-substituted phosphanes 11. The 31P-NMR spectra of 11
each contain a singlet in the region typical for stannyl-sub-
1
stituted phosphanes[7] with JP,
coupling constants of
117,119Sn
ca. 720 Hz. In the proton-coupled 31P-NMR spectra these
lents of the phosphaalkyne 8. The proposed compositions
of the products were further supported by elemental analy-
ses or high-resolution mass spectrometry. The 31P-NMR
spectra each reveal the typical AX spin system for 1,2-di-
hydro-1,3-diphosphetes[8][9]. The signals for the λ3σ2-phos-
phorus atoms occur in the expected low-field positions (δ ϭ
369Ϫ376) while those of the λ3σ3-phosphorus atoms are
found at δ ϭ Ϫ5 to ϩ3. Both signals experience 2JP,P coup-
lings of 35 to 44 Hz and appear as doublets. Thus, the ex-
istence of the structurally isomeric 1,4-dihydro-1,2-diphos-
phetes can be excluded on the basis of the small P,P coup-
lings[10]. In the proton-undecoupled 31P-NMR spectra the
signals for the λ3σ3-phosphorus atom are further split by
1JP,H couplings and those of the λ3σ2-phosphorus atoms by
3JP,H couplings to give a doublet of doublets. A comparison
of the measured values with those of previously known 1,2-
dihydro-1,3-diphosphetes[8][11][12] supports the proposed
constitutions. The 13C-NMR spectra provide further di-
agnostic evidence. The doublet of doublets with large (ca.
1
signals are split into doublets by JP,H couplings of ca. 200
Hz. In the 1H-NMR spectra doublet signals at δ ϭ
1
3.03Ϫ3.32 with appropriate JH,P coupling constants are
observed for the PH function while the protons added to
carbon atoms give rise to signals at δ ϭ 2.86Ϫ2.94. The
2JH,P coupling constants of about 4 Hz are very small. Inte-
gration of the individual signal groups clearly shows the 1:2
ratio of phosphaalkyne 8 to tin hydride 1b. The presence of
the PH function is further supported by a valency vibration
at 2240 cmϪ1 in the IR spectra. The presence of two non-
equivalent tin atoms is also apparent from the 119Sn-NMR
spectra. The triphenylstannyl groups directly bonded to
phosphorus give doublet signals at δ ϭ Ϫ73/Ϫ75 with 1JSn,P
coupling constants of ca. 730 Hz, while the signals of C-
bonded tin atoms appear as singlets at δ ϭ Ϫ104. Identifi-
cation of the phosphanes 12a؊c, which were not isolated,
was based on direct 31P-NMR-spectroscopic investigation
of the reaction solutions. The chemical shifts of δ ϭ Ϫ136.4
1
(12a), Ϫ143.7 (12b), and Ϫ138.1 (12c), as well as the JP,H
coupling constants [198.1 Hz (12a), 198.8 Hz (12b), 216.6
Hz (12c)], support the proposed structures.
1
50 Hz) and small (ca. 20 Hz) JC,P coupling constants ob-
served at low field is characteristic for the skeletal sp2 car-
bon atoms[13]. The second skeletal carbon atoms give rise
to signals in the typical sp3 region with appreciably smaller
The phosphaalkenes 9 may be postulated as reactive in-
1JC,P coupling constants. The varying chemical shifts of the termediates in these stoichiometry-dependent reactions.
tin atoms in the 119Sn-NMR spectra can be rationalized in These species then undergo stabilization either in a formal
terms of the differing substitution: The tin atoms of the [2 ϩ 2] cycloaddition to give the 1,2-dihydro-1,3-diphos-
tributyl-substituted derivatives give rise to signals in the re- phetes 10 or by renewed 1,2-addition of a further equivalent
gion typical for tetraalkyl-substituted tin compounds[14] of tin hydride 1 to furnish the phosphanes 11 and 12. The
while increasing phenyl substitution results in a stepwise preferential formation of the phosphanes 11 over 12 can be
shift to higher field[15]
.
rationalized in terms of both steric and electronic factors.
228
Eur. J. Inorg. Chem. 1998, 227Ϫ235

Organophosphorus Compounds, 125
FULL PAPER
The 1H-, 13C-, 31P-NMR, and IR data for the 1,2-di-
hydro-1,3-diphosphetes 16b, c were taken from the crude
reaction solutions and are in good agreement with those of
the 1,2-dihydro-1,3-diphosphetes 10. Thus, a detailed dis-
cussion of these data and the mechanism of the formation
of the products is unnecessary in the light of the infor-
mation given in the previous section.
Reactions with Diorganotin Dihydrides
When the diorganotin dihydrides 13a, b are allowed to
react with an appreciable excess of the phosphaalkyne 8a
the primary products are the 1,2-dihydro-1,3-diphosphetes
14a, b. However, these species undergo an unspecific de-
composition so that their isolation is not possible. Even so,
they can be characterized by 31P-NMR and IR spec-
troscopy through termination of the reaction after 24 hours
and removal of the volatile tin hydrides 13a, b together with
the excess phosphaalkyne 8a under vacuum (oil pump).
The constitution of the cage compound 17c was sup-
ported by mass spectrometry and elemental analysis. Link-
age of the four phosphaalkyne units gives rise to an A2MX
spin system in the 31P-NMR spectrum. As a consequence
of the CS symmetry, the phosphorus atoms P1 and P3 are
magnetically equivalent (δ ϭ 221). The signals for P5 and
P7 appear at δ ϭ 184 and δ ϭ Ϫ72. The unusually low-
field signals for the λ3σ3-phosphorus atoms P1, P3, and P5
are, in fact, not surprising when one considers that the
pentacyclic compound 17c is formally derived from tetra-
phosphacubane, which gives a 31P-NMR signal at δ ϭ
257[18]. These values can be explained on the basis of the
bonding model derived for tetraphosphacubane, which re-
veals a strong interaction between the lone elctron pairs of
the phosphorus atoms and the phosphorus-carbon σ bonds
of the cubane skeleton. This effect is responsible for the
dramatic low-field shifts of the phosphorus signals as well
as the extreme high-field shifts of the signals for the skeletal
carbon atoms in the 13C-NMR spectrum[19]. A further indi-
cation in favor of the proposed structure is given by the
tin satellite lines in the 31P-NMR spectrum: P7 exhibits a
characteristic 1JP,Sn coupling of 744 Hz, clearly demonstrat-
ing that P7 and tin are directly adjacent[20]. Tin satellites
The spectroscopic data of these compounds are in good
agreement with those of the 1,2-dihydro-1,3-diphosphetes
10 discussed above. Therefore the constitutions of these
hydrostannylation products may be considered as certain.
One special feature resulting from the presence of the tin
hydride function should be mentioned: The IR spectra con-
tain SnH valency vibrations at 1790/1800 cmϪ1 in addition
to the PH valency vibrations. This tin hydride function is
presumably the cause of the unspecific decomposition reac-
tions.
3
with JP,Sn coupling constants of 109 Hz are observed for
Reactions with Chlorodiorganotin Hydrides
the signal of P5. Accordingly, the 119Sn-NMR signal for the
Reactions of the chlorodiorganotin hydrides 4 with the
phosphaalkyne 8a proceed much less selectively than those
with the triorganotin hydrides 1. In addition to the 1,2-di-
hydro-1,3-diphosphetes 16b, c formed as main products, nu-
merous by-products are observed by 31P-NMR-spectros-
copic monitoring of the reaction solutions. One of these by-
products is the cage compound 17. Product 17b cannot be
isolated, while 17c has been isolated in pure form by crystal-
lization from pentane at Ϫ20°C and completely charac-
terized. Complete separation of the reaction mixtures into
their components by either column chromatography or
bulb-to-bulb distillation was not possible.
tin atom (δ ϭ 328) is split into a doublet of doublets
3
(1JP,
ϭ 784 Hz, J
ϭ 113 Hz). As a consequence of
119
119
Sn
Sn
P,
the CS symmetry the 1H-NMR spectrum contains only
three signals for the four tert-butyl groups, with an intensity
ratio of 1:2:1. For the same reason the skeletal carbon
atoms C4 and C6 are magnetically equivalent in the 13C-
1
NMR spectrum (pt, δ ϭ 37.6, JC,P ϭ 13.5 Hz). Carbon
atom C2 gives, as required by the discussed bonding model,
a signal at extremely high field (δ ϭ Ϫ17.2) (cf. skeletal
carbon atom signals of tetraphosphacubane:
δ
ϭ
Ϫ29.1)[18][19]. Finally, the skeletal carbon atom C9 produces
a
13C-NMR signal at δ ϭ 22.7.
From a mechanistic point of view, the formation of the
cage compounds 17 may be considered as a cyclooligomer-
ization of the phosphaalkyne 8a in the coordination sphere
of tin. Since the reaction of the 1,2-dihydro-1,3-diphosphete
16c with an excess of the phosphaalkyne 8a does not lead
to the formation of the homocubane 17c, the existence of
the 1,2-dihydro-1,3-diphosphete 16c as an intermediate can
be discounted. Similarly, subsequent attempts to introduce
the stannyl unit into a skeletal bond of tetraphosphacub-
ane[18] by reaction of the latter with dibutyl(chloro)tin hy-
dride (4b) were unsuccessful. Thus, a plausible mechanism
involves the stepwise construction of the P/C skeleton by
oligomerization of the phosphaalkyne units at tin.
Eur. J. Inorg. Chem. 1998, 227Ϫ235
229

M. Schmitz, R. Göller, U. Bergsträßer, S. Leininger, M. Regitz
FULL PAPER
Figure 1. Molecular structure of 18d[a]
Thermal Isomerization of the 1,2-Dihydro-1,3-diphosphetes 10
After heating of the 1,2-dihydro-1,3-diphosphetes 10a؊d
in toluene at 90°C for 6 hours, quantitative isomerization
of the original 2-stannyl-substituted 1,2-dihydro-1,3-dipho-
sphetes into the 1-stannyl-substituted derivatives 18a؊d is
observed.
[a]
The natures of the 1,2-dihydro-1,3-diphosphetes 18 ob-
tained were unequivocally demonstrated by mass spec-
trometry and elemental analysis. Evidence for the arrange-
ment of the substituents was provided by analysis of the
NMR spectra in comparison with the data for the starting
compounds 10a؊d. Thus, the 31P-NMR signals of the λ3σ2-
phosphorus atoms experienced high-field shifts of almost
20 ppm, while the signals of the λ3σ3-phosphorus atoms
changed only slightly (δ ϭ 2Ϫ3). The direct adjacency of
Selected bond lengths [pm] and angles [°]: P(1)-C(2) 181.5(4),
P(1)-C(1) 188.7(4), P(2)-C(2) 169.7(4), P(2)-C(1) 187.1(4), Sn(1)-
C(21) 214.5(4), Sn(1)-C(31) 214.2(4), Sn(1)-C(11) 215.1(4), Sn(1)-
P(1) 252.84(12); C(2)-P(1)-C(1) 82.2(2), C(2)-P(2)-C(1) 85.9(2),
P(2)-C(1)-P(1) 91.2(2), P(2)-C(2)-P(1) 99.7(2), C(41)-C(1)-P(1)
118.1(3), C(41)-C(1)-P(2) 118.7(3), C(61)-C(2)-P(1) 130.0(3), C(61)-
C(2)-P(2) 130.0(3), C(11)-Sn(1)-P(1) 115.27(12), C(21)-Sn(1)-P(1)
103.33(10), C(31)-Sn(1)-P(1) 113.14(10).
Complexation Behavior of 10
Phosphane ligands have found a wide range of appli-
cations in organometallic chemistry[23][24]. A common
method for the preparation of phosphorus-containing tran-
sition-metal complexes comprises of a ligand-exchange re-
action between phosphorus compounds and carbonyl tran-
sition-metal complexes.
In the case of the 1,2-dihydro-1,3-diphosphetes 10, both
complexation of one phosphorus atom (Ǟ 19) and com-
plete complexation of both phosphorus atoms (Ǟ 20) are
possible using W(CO)5·THF. Reactions of the 1,2-dihydro-
1,3-diphosphetes 10a, b with excess Fe2(CO)9 furnish the
doubly complexed derivatives 21a, b.
tin to phosphorus is apparent from the tin satellites at the
1
117,119
signal of P1 with JP, Sn coupling constants of more than
3
117,119Sn
1000 Hz and the markedly smaller JP,
coupling con-
stants of 170 Hz at P3. The same couplings also appear in
the 119Sn-NMR spectra. Because of the migration of the
1
hydrogen atom from phosphorus to carbon the H-NMR
signal of this proton experiences a pronounced diamagnetic
shift from δ ϭ 7.5 to 2.6 and, instead of the original split-
ting into a doublet of doublets, appears merely as a doublet
2
with a small JH,P coupling of 1.4 Hz. The magnitude of
2
this JH,P coupling can be interpreted as evidence for the
trans arrangement of 18[21]. In the 13C-NMR spectra the
skeletal carbon atoms C4 give the expected doublet of
2
doublet signals at low field (δ ϭ 238.1Ϫ240.4; JC,P ϭ 53/
40 Hz) while the signals of the second skeletal carbon atom
appear as doublets (1JC,P ϭ 22 to 24 Hz) at δ ϭ 36.4Ϫ39.1
in the typical sp3 region. An X-ray crystallographic analysis
of product 18d (Figure 1) supplied final confirmation of the
trans orientation of the adamantyl group and the tri-
phenylstannyl group. Since only one isomer was obtained
from each experiment and since the λ3σ3-phosphorus atoms
should be configurationally stable[16], the same arrange-
ment of the substituents can also safely be assumed for the
compounds 18a؊c.
The four-membered diphosphacyclobutene ring deviates
slightly from planarity (sum of internal angles: 358.9°). The
dihedral angle between the planes C(1)ϪP(1)ϪC(2) and
C(1)ϪP(2)ϪC(2) amounts to 10.7°. The P(2)ϪC(2) bond
length of 169.7 pm is in the typical range for PϪC double
bonds[22], whereas the P(1)ϪC(2) single bond is somewhat
shortened to 181.5 pm. The tin atom exists in a distorted
tetrahedral environment.
230
Eur. J. Inorg. Chem. 1998, 227Ϫ235

Organophosphorus Compounds, 125
FULL PAPER
1,2-Dihydro-1,3-diphosphetes 10. Ϫ General Procedure: To a solu-
tion of phosphaalkyne 8 in pentane was added the tin hydride 1.
The mixture was stirred for two weeks at room temperature and
the solvent removed under vacuum. The residue was purified by
chromatography or crystallization.
The spectroscopic characterization of the complexes 19,
20, and 21 is relatively simple. For the pentacarbonyltung-
sten complexes 19 and 20 the η1 coordination of the metal
fragment at P1 (for compound 19) or at P1 and P3 (for
compound 20) is impressively demonstrated by the charac-
teristic P-W couplings[25] in the 31P-NMR spectra. The
complexation has only a minor influence on the 13C-NMR
data of the starting materials with additional characteristic
signals being observed at low field for the carbonyl groups
(see Experimental Section). Furthermore, CO valency vi-
brations appear in the IR spectra of compounds 19, 20, and
2,4-Di-tert-butyl-2-tributylstannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (10a): From 8a (800 mg, 8 mmol) in pentane (3 ml)
and 1a (873 mg, 3 mmol); chromatography on aluminum oxide (5%
H2O) with pentane yielded 10a (413 mg, 28%) as a yellow, non-
1
distillable oil. Ϫ H NMR (C6D6): δ ϭ 0.65Ϫ1.94 (m, 45 H, Bu-H
1
3
and tBu-H), 6.73 (dd, JH,P ϭ 164.7 Hz, JH,P ϭ 21.5 Hz, 1 H,
PϪH). Ϫ 13C{1H} NMR (C6D6): δ ϭ 13.5 (s, JC,
ϭ 315.7
1
117/119Sn
21. The compositions of the products were further substan- Hz, SnϪCH2), 13.9 (s, SnϪ[CH2]3ϪCH3), 28.0 (s, SnCH2CH2),
29.7 [dd, 3JC,P ϭ 10.1/5.8 Hz, C(CH3)3], 30.0 (s, CH2CH3), 30.8 [d,
tiated by mass spectrometry and elemental analysis.
1
3JC,P ϭ 5 Hz, C(CH3)3], 36.4 (dd, JC,P ϭ 39.2/5.5 Hz, C2), 37.1
2
2
[d, JC,P ϭ 7.7 Hz, C(CH3)3], 39.8 [d, JC,P ϭ 6.3 Hz, C(CH3)3],
Reaction of 10 with Iodine
222.56 (dd, JC,P ϭ 52.1/23.2 Hz, C4). Ϫ 31P{1H} NMR (C6D6):
1
2
2
Conversion of the PH function of the 1,2-dihydro-1,3-
diphosphete 10b into a PI function can be achieved by
treatment of 10b with a solution of iodine in diethyl ether
at room temperature.
δ ϭ 0.7 (d, JP,P ϭ 39.1 Hz, P-1), 375.6 (d, JP,P ϭ 39.1 Hz, P-3).
Ϫ
119Sn{1H} NMR (C6D6): δ ϭ 3.85 (s). Ϫ IR (film): ν˜ ϭ 2940,
2910, 2860, 2200 (PϪH), 1455, 1355, 1210, 1110, 840 cmϪ1. Ϫ MS;
m/z (%): 492 (13) [Mϩ], 291 (39) [SnBu3ϩ], 235 (76) [HSnBu2ϩ],
179 (100) [H2SnBuϩ], 57 (38) [C4H9ϩ]. Ϫ C22H46P2Sn (491.26):
calcd. C 53.8, H 9.4; found C 53.6, H 9.3.
2,4-Di-tert-butyl-2-triphenylstannyl-1,2-dihydro-1λ3,3λ3-di-
phosphete (10b): From 8a (4 g, 40 mmol) in pentane (5 ml) and 1b
(3.43 g, 9.8 mmol); crystallization from 3 ml of pentane at Ϫ20°C
yielded 10b (2.6 g, 48% based on 1b) as a yellow solid with m.p.
1
68°C. Ϫ H NMR (C6D6): δ ϭ 1.16 (s, 9 H, tBu-H), 1.65 (s, 9 H,
tBu-H), 7.42Ϫ7.48 (m, 9 H, m-, p-C6H5), 7.57 (dd, 1JH,P ϭ 166 Hz,
3JH,P ϭ 18.6 Hz, 1 H, PϪH), 8.05Ϫ8.08 (m, 6 H, o-C6H5). Ϫ
13C{1H} NMR (C6D6): δ ϭ 29.9 [d, 3JC,P ϭ 3.6 Hz, C(CH3)3], 30.3
The degradation of the PH function is immediately de-
monstrated by the absence of the corresponding signal in
the 1H-NMR spectrum. Also, no P,H couplings can be seen
in the proton-coupled 31P-NMR spectrum. In comparison
to that of the starting material the 13C-NMR signal for C2
experiences a shift of almost 20 ppm to lower field. Finally,
the increases in the 1JC,P coupling constants are noteworthy.
The composition of the 1,2-dihydro-1,3-diphosphete 22 was
substantiated by mass spectrometry and elemental analysis.
3
2
[d, JC,P ϭ 9.0 Hz, C(CH3)3], 37.4 [d, JC,P ϭ 7.2 Hz, C(CH3)3],
39.2 (dd, 1JC,P ϭ 38.2/4 Hz, C2), 39.6 [d, 2JC,P ϭ 5.4 Hz, C(CH3)3],
2
3
117/119Sn
128.7 (s, JC,
ϭ 49.4 Hz, o-C), 129.2 (s, p-C), 138.0 (s,
1
117/119Sn
JC,
117/119Sn
ϭ 471.2/492.8 Hz,
ϭ 35.0 Hz, m-C), 141.6 (s, JC,
ipso-C), 224.4 (dd, JC,P ϭ 51.6/22.9 Hz, C4). Ϫ 31P{1H} NMR
1
2
2
(C6D6): δ ϭ 2.5 (d, JP,P ϭ 35.8 Hz, P-1), 372.1 (d, JP,P ϭ 35.8
Hz, P-3). Ϫ Sn{1H} NMR (C6D6): δ ϭ Ϫ99.75 (pt, J
ϭ
119
2
119Sn,P
24.4 Hz). Ϫ IR (KBr): ν˜ ϭ 3040, 2920, 2180 (PϪH), 1450, 1410,
1350, 1100, 840 cmϪ1. Ϫ MS; m/z (%): 552 (5) [Mϩ], 351 (100)
[SnPh3ϩ], 197 (24) [SnPhϩ], 57 (18) [C4H9ϩ]. Ϫ C28H34P2Sn
(551.23): calcd. C 61.0, H 6.2; found C 61.3, H 6.2.
We thank the Fonds der Chemischen Industrie for generous finan-
cial support. We are also grateful to the Deutsche Forschungsge-
meinschaft (Graduate College Phosphorus as Connecting Link Be-
tween Various Chemical Disciplines) for generous financial support
and a post-graduate grant (to M. S.).
2,4-(Diadamant-1-yl)-2-tributylstannyl-1,2-dihydro-1λ3,3λ3-di-
phosphete (10c): From 8b (360 mg, 2 mmol) in pentane (2 ml) and
1a (291 mg, 1 mmol); after stirring the reaction mixture for two
weeks at room temperature the solution was heated to 60°C for 4
h; chromatography on aluminum oxide (5% H2O) with pentane
yielded 10c (150 mg, 23%) as a yellow, non-distillable oil. Ϫ 1H
NMR (C6D6): δ ϭ 1.10Ϫ2.62 (m, 57 H, Ad-H and Bu-H), 6.81
Experimental Section
General: All experiments were carried out under argon (purity:
> 99.998%) in previously evacuated and oven-dried Schlenk vessels.
The solvents were anhydrous and stored under argon. Ϫ Melting
points: Mettler FP 61 (heating rate: 3°C/min), uncorrected. Ϫ El-
(dd, 1JH,P ϭ 164 Hz, 3JH,P ϭ 22 Hz, 1 H, PϪH). Ϫ 13C{1H} NMR
1
1
117/119Sn
(C6D6): δ ϭ 13.8 (s, JC,
ϭ 313.8 Hz, SnϪCH2), 13.9 (s,
Sn ϭ 63.0 Hz, SnCH2CH2), 29.2
emental analyses: Perkin-Elmer EA 240. Ϫ H NMR: Varian EM
SnϪ[CH2]3ϪCH3), 28.1 (s, 2JC,
117/119
360 (60 MHz), Bruker AC 200 and AMX 400; chemical shifts are
relative to the solvent signals, and converted to TMS. Ϫ 13C NMR:
Bruker AC 200 and AMX 400; chemical shifts are relative to the
solvent signals. Ϫ 31P NMR: Bruker AC 200, external standard
H3PO4. Ϫ MS: Finnigan MAT 90 (70 eV). Ϫ IR: Perkin-Elmer
16 PC FT-IR and Perkin-Elmer 1310. Ϫ Chemicals: Triphenyltin
hydride (1b) was prepared from triphenyltin chloride[26], dimeth-
yltin dihydride (13a)[27], dipropyltin dihydride (13b)[28], dibutyltin
dihydride (13c)[29], dipropyltin dichloride (15b)[30], and the phos-
phaacetylenes 8a[31], b[32], c[31] were prepared as described in the
literature. All other starting materials were purchased from com-
mercial suppliers.
(s, C-c), 29.5 (s, C-c), 30.2 (s, 3JC,
ϭ 35.3 Hz, CH2CH3), 37.0
117/119
Sn
1
2
(s, 2 ϫ C-d), 37.4 (d, JC,P ϭ 30.5 Hz, C-2), 38.9 (d, JC,P ϭ 6.3
Hz, C-a), 41.2 (br. d, 3JC,P ϭ 7.6 Hz, C-b), 42.1 (d, 2JC,P ϭ 5.7 Hz,
3
1
C-a), 43.5 (d, JC,P ϭ 3.8 Hz, C-b), 222.6 (dd, JC,P ϭ 51/22.4 Hz,
C-4). Ϫ 31P{1H} NMR (C6D6): δ ϭ Ϫ5.2 (d, JP,P ϭ 43.6 Hz,
2
P-1), 373.3 (d, 2JP,P ϭ 43.6 Hz, P-3). Ϫ IR (film): ν˜ ϭ 2920Ϫ2800,
2160 (PϪH), 1440, 1320, 1270, 1140 cmϪ1. Ϫ MS; m/z (%): 649
(36) [Mϩ], 291 (46) [SnBu3ϩ], 135 (100) [Adϩ]. Ϫ C34H58P2Sn
(647.49): calcd. C 63.1, H 9.0; found C 63.4, H 8.9.
2,4-(Diadamant-1-yl)-2-triphenylstannyl-1,2-dihydro-1λ3,3λ3-di-
phosphete (10d): From 8b (300 mg, 1.7 mmol) in pentane (5 ml)
Eur. J. Inorg. Chem. 1998, 227Ϫ235
231

M. Schmitz, R. Göller, U. Bergsträßer, S. Leininger, M. Regitz
FULL PAPER
and 1b (296 mg, 0.8 mmol); evaporation of the solvent and washing 20°C, the solvent removed under vacuum, and the residue washed
of the residue with pentane yielded 10d (198 mg, 35%) as a yellow several times with pentane.
1
solid with m.p. 92°C. Ϫ H NMR (C6D6): δ ϭ 1.38Ϫ2.63 (m, 30
[tert-Butyl(triphenylstannyl)methyl]triphenylstannylphosphane
(11a): From 8a (0.4 g, 4 mmol) in pentane (5 ml) and 1b (6.32 g,
1
H, Ad-H), 7.20Ϫ7.41 (m, 9 H, m-, p-C6H5), 7.44 (dd, JH,P ϭ 168
3
Hz, JH,P ϭ 21 Hz, 1 H, PϪH), 7.87Ϫ8.09 (m, 6 H, o-C6H5). Ϫ
18 mmol) to furnish 11a (2.6 g, 81%) as a pale yellow powder with
13C{1H} NMR (C6D6): δ ϭ 28.9 (s, C-c), 29.2 (s, C-c), 36.5 (s, C-
m.p. 154°C. Ϫ 1H NMR (C6D6): δ ϭ 1.04 (s, 9 H, tBu), 2.94 (d,
2
3
d), 36.7 (s, C-d), 39.1 (d, JC,P ϭ 6.5 Hz, C-a), 41.6 (br. d, JC,P
ϭ
1
2JH,P ϭ 4.5 Hz, 1 H, PCϪH), 3.32 (d, JH,P ϭ 196.2 Hz, 1 H,
2
3
10.0 Hz, C-b), 41.9 (d, JC,P ϭ 5.6 Hz, C-a), 42.1 (d, JC,P ϭ 5.6
PϪH), 7.05Ϫ7.13 (m, 18 H, m-, p-C6H5), 7.47Ϫ7.49 (m, 6 H, o-
Hz, C-b), 128.7 (s, 2JC,
Sn ϭ 49.0 Hz, o-C), 129.0 (s, p-C), 138.2
117/119
C6H5), 7.62Ϫ7.66 (m, 6 H, o-C6H5). Ϫ 13C{1H} NMR (C6D6): δ ϭ
3
1
117/119Sn
(s, JC,
117/119Sn
ϭ 467.4/489.1
ϭ 35.3 Hz, m-C), 142.2 (s, JC,
1
1
28.8 (d, 1JC,P ϭ 36.1 Hz, PCH, H coupl.: JC,H ϭ 129.3 Hz), 32.4
1
Hz, ipso-C), 223.9 (dd, JC,P ϭ 50.2/21.3 Hz, C-4), the C-2 signal
3
2
[d, JC,P ϭ 10.4 Hz, C(CH3)3], 35.4 [d, JC,P ϭ 17.7 Hz, C(CH3)3],
129.26 (s, o-C), 129.30 (s, o-C), 129.4 (s, p-C), 129.6 (s, p-C), 137.9
could not be detected because of signal overlap. Ϫ 31P{1H} NMR
2
2
(C6D6): δ ϭ Ϫ4.1 (d, JP,P ϭ 43 Hz, P-1), 369.2 (d, JP,P ϭ 43 Hz,
P-3). Ϫ 119Sn{1H} NMR (C6D6): δ ϭ Ϫ101.43 (s). Ϫ IR (KBr):
ν˜ ϭ 3030, 2940, 2865, 2818, 2180 (PϪH), 1432, 1413, 1330, 1295,
1249, 715, 685 cmϪ1. Ϫ MS; m/z (%): 708 (6) [Mϩ], 351 (100) [SnPh
2
(s, m-C), 138.1 (s, m-C), 139.1 (d, JC,P ϭ 4 Hz, ipso-C), 140.2 (s,
ipso-C). Ϫ 31P{1H} NMR (C6D6): δ ϭ Ϫ170 (s, JP,
ϭ 716
1
117,119Sn
Hz). Ϫ Sn{1H} NMR (C6D6): δ ϭ Ϫ73 (d, J
ϭ 732 Hz,
119
1
119Sn,P
PϪSn), Ϫ104 (s, PCϪSn). Ϫ IR (KBr): ν ϭ 3030, 2920, 2240
˜
ϩ], 135 (47) [Adϩ]. Ϫ C40H46P2Sn (707.5): calcd. C 67.9, H 6.6;
3
(PϪH), 1460, 1410, 1350, 1320, 1285, 1250, 1210, 1180, 1060, 1010,
985, 855, 750, 715, 685 cmϪ1. Ϫ MS; m/z (%): 802 (0.2) [Mϩ], 451
(2) [Mϩ Ϫ SnPh3], 351 (100) [SnPh3ϩ], 197 (18) [SnPhϩ], 57 (9)
[C4H9ϩ]. Ϫ C41H41PSn2 (802.14): calcd. C 61.4, H 5.2; found C
61.4, H 5.2.
found C 67.6, H 6.5.
2,4-Di-tert-pentyl-2-tributylstannyl-1,2-dihydro-1λ3,3λ3-di-
phosphete (10e): From 8c (357 mg, 3.13 mmol) in pentane (5 ml)
and 1a (407 mg, 1.4 mmol); chromatography on aluminum oxide
(5% H2O) with pentane yielded 10e (540 mg, 74%) as a yellow,
[Adamant-1-yl(triphenylstannyl)methyl]triphenylstannylphos-
phane (11b): From 8b (0.3 g, 1.66 mmol) in pentane (5 ml) and 1b
(3.16 g, 9 mmol) to furnish 11b (1.01 g, 75%) as a colorless powder
1
non-distillable oil. Ϫ H NMR (C6D6): δ ϭ 0.86Ϫ1.59 (m, 45 H,
1
3
tPent-H and Bu-H), 6.78 (dd, JH,P ϭ 163.04 Hz, JH,P ϭ 20.27
Hz, 1 H, PϪH). Ϫ 13C{1H} NMR (C6D6): δ ϭ 8.0 (s, 1JC,
Sn ϭ
117/119
1
with m.p. 185°C (dec.). Ϫ H NMR (C6D6): δ ϭ 1.2Ϫ1.9 (m, 15
341.3 Hz, SnϪCH2), 9.2 (s, CH2CH3), 9.6 (s, CH2CH3), 13.5 (s,
2
1
H, Ad-H), 2.86 (d, JH,P ϭ 3.7 Hz, 1 H, PCϪH), 3.03 (d, JH,P
ϭ
3
SnϪ[CH2]3ϪCH3), 24.7 [br. d, JC,P ϭ 6.4 Hz, C(CH3)2], 25.8 [br.
198.4 Hz, 1 H, PϪH), 6.9Ϫ7.25 (m, 18 H, m-, p-C6H5), 7.3Ϫ7.8
3
d, JC,P ϭ 8.0 Hz, C(CH3)2], 27.1 (s, SnCH2CH2), 29.9 [s,
(m, 12 H, o-C6H5). Ϫ 13C{1H} NMR (C6D6): δ ϭ 31.3 (s, C-c),
3
3
117/119
JC,
ϭ 21.7 Hz, Sn(CH2)2CH2CH3], 34.7 (dd, JC,P ϭ 9.2/4.4
1
31.4 (d, JC,P ϭ 39.4 Hz, PCH, 1H coupl.: 1JC,H ϭ 127.7 Hz), 38.2
Sn
Hz, CH2CH3), 35.4 [d, 2JC,P ϭ 7.2 Hz, C(CH3)2CH2CH3], 36.1 (dd,
2
3
(d, JC,P ϭ 15.2 Hz, C-a), 38.6 (s, C-d), 46.7 (d, JC,P ϭ 11.1 Hz,
C-b), 130.7 (s, o-C), 130.9 (s, o-C), 131.0 (s, p-C), 131.2 (s, p-C),
3JC,P ϭ 7.2/4.0 Hz, CH2CH3), 38.4 (d, JC,P ϭ 40.2 Hz, C2), 39.2
1
[d, 2JC,P ϭ 6.4 Hz, C(CH3)2CH2CH3], 221.0 (dd, 1JC,P ϭ 52.2, 24.1
2
139.4 (s, m-C), 139.7 (s, m-C), 140.9 (d, JC,P ϭ 3.3 Hz, ipso-C),
Hz, C-4). Ϫ 31P{1H} NMR (C6D6): δ ϭ 1 (d, JP,P ϭ 41 Hz, P-1),
2
142.8 (s, ipso-C). Ϫ 31P{1H} NMR (C6D6): δ ϭ Ϫ175 (s,
379 (d, 2JP,P ϭ 41 Hz, P-3). Ϫ IR (pentane): ν˜ ϭ 2942, 2912, 2880,
2340 (PϪH), 1644, 1456 cmϪ1. Ϫ MS; m/z (%): 520 (5) [Mϩ], 291
(100) [SnBu3ϩ], 235 (59) [HSnBu2ϩ], 177 (60) [SnBuϩ], 71 (44)
[C(CH)3CH2CH3ϩ], 57 (16) [C4H9ϩ]. Ϫ HR-MS: C24H50P2Sn:
calcd. 520.2409; found 520.2385.
1JP,
1J
ϭ 724 Hz). Ϫ 119Sn{1H} NMR (C6D6): δ ϭ Ϫ75 (d,
ϭ 731 Hz, PϪSn), Ϫ104 (s, PCϪSn). Ϫ IR (KBr): ν ϭ
117,119Sn
119Sn,P
˜
3030, 2910, 2840, 2240 (PϪH), 1480, 1425, 1310, 1100, 1070, 1020,
1000, 890, 730, 700 cmϪ1. Ϫ C47H47PSn2 (880.25): calcd. C 64.1,
H 5.4; found C 64.0, H 5.3.
2,4-Di-tert-pentyl-2-triphenylstannyl-1,2-dihydro-1λ3,3λ3-di-
phosphete (10f): From 8c (422 mg, 3.7 mmol) in pentane (5 ml) and
1b (123 mg, 0.35 mmol); evaporation of the solvent and washing
1,2-Dihydro-1,3-diphosphetes 14a, b. Ϫ General Procedure: To a
solution of phosphaalkyne 8 in pentane was added the diorganotin
dihydride 13 and the mixture stirred at room temperature for 24 h.
The solvent, unreacted phosphaalkyne 8, and tin hydride 13 were
removed under vacuum. Further purification by distillation, chro-
matography, or crystallization was not possible.
of the residue with pentane yielded 10f (70 mg, 34%) as a yellow
3
solid with m.p. 86°C. Ϫ 1H NMR (C6D6): δ ϭ 0.70 (t, JH,H
ϭ
3
7.24 Hz, 3 H, CH2CH3), 0.82 (t, JH,H ϭ 7.87 Hz, 3 H, CH2CH3),
0.86 [s, 3 H, C(CH3)2], 0.88 [s, 3 H, C(CH3)2], 1.27 [s, 3 H,
C(CH3)2], 1.29 [s, 3 H, C(CH3)2], 7.10Ϫ7.18 (m, 9 H, m, p-C6H5),
7.27 (dd, JH,P ϭ 166.59 Hz, JH,P ϭ 19.98 Hz, 1 H, PϪH),
7.73Ϫ7.82 (m, 6 H, o-C6H5). Ϫ 13C{1H} NMR (C6D6): δ ϭ 9.1 (s,
CH2CH3), 9.5 (s, CH2CH3), 24.8 [br. s, C(CH3)2], 25.1 [br. s,
C(CH3)2], 35.2 (br. s, CH2CH3), 35.8 (br. s, CH2CH3), 39.7 (d,
2,4-Di-tert-butyl-2-hydridodimethylstannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (14a): From 8a (800 mg, 8 mmol) in pentane and 13a
(452 mg, 3 mmol) to furnish 14a (70 mg, 7%) as a yellow oil. Ϫ
1
3
1
2
31P{1H} NMR (C6D6): δ ϭ 1.9 (dd, JP,H ϭ 161.5 Hz, JP,P ϭ 40.9
2
3
Hz, P-1), 371.5 (dd, JP,P ϭ 40.9 Hz, JP,H ϭ 18.5 Hz, P-3). Ϫ IR
(film): ν ϭ 2930, 2910, 2170 (PϪH), 1790 (SnϪH), 1450, 1350,
˜
1JC,P
ϭ
6.7 Hz, C2)
, 41.3 [s, C(CH3)2CH2CH3], 42.5 [s,
1250, 1240, 1050, 1010, 860, 830, 760, 620 cmϪ1
.
C(CH3)2CH2CH3], 128.4 (s, o-C), 128.8 (s, p-C), 137.8 (s,
1
3JC,
ϭ 34.4 Hz, m-C), 141.6 (s, ipso-C), 222.7 (dd, JC,P ϭ
117/119Sn
2,4-Di-tert-butyl-2-hydridodipropylstannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (14b): From 8a (800 mg, 8 mmol) in pentane and 13b
(620 mg, 3 mmol) to furnish 14b (110 mg, 9%) as a yellow oil. Ϫ
52.0, 22.4 Hz, C-4). Ϫ 31P{1H} NMR (C6D6): δ ϭ 3 (d, JP,P ϭ 40
Hz, P-1), 376 (d, JP,P ϭ 40 Hz, P-3). Ϫ IR (pentane): ν˜ ϭ 2990,
2
2
2199 (PϪH), 1468, 1429, 1261, 1072, 1021, 807, 726 cmϪ1. Ϫ MS;
m/z (%): 580 (1) [Mϩ], 351 (100) [SnPh3ϩ], 274 (20) [SnPh2ϩ], 197
(62) [SnPhϩ], 77 (20) [C6H5ϩ], 71 (13) [C(CH3)2CH2CH3ϩ]. Ϫ HR-
MS: C30H38P2Sn: calcd. 580.1470; found 580.1465.
1
2
31P{1H} NMR (C6D6): δ ϭ Ϫ0.4 (dd, JP,H ϭ 163 Hz, JP,P ϭ 41
2
3
Hz, P-1), 369.7 (dd, JP,P ϭ 41 Hz, JP,H ϭ 21 Hz, P-3). Ϫ IR
(film): ν˜ ϭ 3000, 2980, 2920, 2900, 2160 (PϪH), 1800 (SnϪH),
1350, 1250, 1240, 1050, 1010, 860, 830, 770, 750 cmϪ1
.
1,2-Bis(triphenylstannyl)phosphanes 11a, b.
cedure: To a solution of phosphaacetylene 8 in pentane was added
triphenyltin hydride (1b). The mixture was stirred for one week at
Ϫ
General Pro-
1,2-Dihydro-1,3-diphosphetes 16 and Homocubane 17. Ϫ General
Procedure: Diorganotin dichloride 15 was dissolved in toluene (3
ml) and pentane (3 ml) and cooled to 0°C. Diorganotin dihydride
232
Eur. J. Inorg. Chem. 1998, 227Ϫ235

Organophosphorus Compounds, 125
FULL PAPER
13 was added and the reaction solution was stirred for 15 min.
Phosphaalkyne 8 was added. After a few hours the color of the
reaction solution changed to red-brown and after 14 d the solvent
was removed under vacuum. The residue was taken up in pentane
1.2 Hz, 1JC,
ϭ
266.1 Hz, SnϪCH2), 14.1 [s,
117/119Sn
3
SnϪ(CH2)3ϪCH3], 27.8 (s, SnCH2CH2), 28.1 [dd, JC,P ϭ 14.0/9.4
Hz, C(CH3)3], 29.9 (s, CH2CH3), 31.0 [dd, JC,P ϭ 9.3/3.9 Hz,
C(CH3)3], 33.6 [d, JC,P ϭ 6.2 Hz, C(CH3)3], 36.4 (d, JC,P ϭ 23.1
3
2
1
2
1
(10 ml). Unreacted diorganotin dihydride 13 was crystallized at Hz, C-2), 40.7 [pt, JC,P ϭ 7.0 Hz, C(CH3)3], 239.8 (dd, JC,P
ϭ
Ϫ20°C, further crystallization at Ϫ20°C yielded the homocubane 51.8/39.9 Hz, C-4). Ϫ 31P{1H} NMR (C6D6): δ ϭ 6.9 (d, JP,P
ϭ
2
1
2
117,119Sn
ϭ 869.9 Hz, P-1), 349.4 (d, JP,P ϭ 39.1 Hz,
17. Compound 17b could not be isolated. It was not possible to
purify the oils which contained the 1,2-dihydro-1,3-diphosphetes
16 as main products.
39.1 Hz, JP,
P-3). Ϫ 119Sn NMR (C6D6): δ ϭ Ϫ36 (dd, 1J
ϭ 916 Hz,
119Sn,P
3
119
J
Sn,P ϭ 147 Hz). Ϫ IR (film): ν˜ ϭ 2950, 2925, 2870, 1470, 1380,
1220, 1125, 860 cmϪ1. Ϫ MS; m/z (%): 492 (9) [Mϩ], 57 (77) [C4H
2,4-Di-tert-butyl-2-chlorodipropylstannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (16b): From 15b (690 mg, 2.5 mmol), 13b (520 mg, 2.5
mmol), and 8a (1600 mg, 16 mmol) to furnish 16b (ca. 85%). Ϫ
1H NMR (C6D6): δ ϭ 0.85Ϫ1.9 (m, 32 H, Pr-H and tBu-H), 6.82
(dd, 1JH,P ϭ 166 Hz, 3JH,P ϭ 20 Hz, 1 H, PϪH). Ϫ 13C{1H} NMR
(C6D6): δ ϭ 18.8 (s, CH2CH3), 20.4 (s, SnCH2CH2), 23.1 (s,
SnCH2), 29.7 [dd, 3JC,P ϭ 9.6/4.8 Hz, C(CH3)3], 30.6 [br. d, 3JC,P ϭ
ϩ]. Ϫ C22H46P2Sn (491.26): calcd. C 53.8, H 9.4; found C 54.0,
9
H 9.3.
trans-2,4-Di-tert-butyl-1-triphenylstannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (18b): From 10b (940 mg, 1.8 mmol) to furnish 18b
(940 mg, 100%) as a yellow powder with m.p. 78°C. Ϫ H NMR
1
(C6D6): δ ϭ 1.17 (s, 9 H, tBu-H), 1.28 (s, 9 H, tBu-H), 2.83 (d,
2
2JH,P ϭ 1.4 Hz, 1 H, PCϪH), 7.21Ϫ7.31 (m, 9 H, m-, p-C6H5),
4.8 Hz, C(CH3)3], 37.1 [br. d, JC,P ϭ 8.0 Hz, C(CH3)3], 40.2 [br.
s, C(CH3)3], 43.2 (dd, 1JC,P ϭ 39.0/6.0 Hz, C-2), 227.6 (dd, 1JC,P ϭ
3
4
3
7.76Ϫ7.79 (dd, JH,H ϭ 7.7 Hz, JH,H ϭ 1 Hz, JH,Sn ϭ 45.8 Hz, 6
53.8/24.1 Hz, C-4). Ϫ 31P{1H} NMR (C6D6): δ ϭ Ϫ5.5 (d, 2JP,P ϭ
H, o-C6H5). Ϫ 13C{1H} NMR (C6D6): δ ϭ 27.8 [dd, JC,P ϭ 7.6/
3
2
3
43.1 Hz, P-1), 365.7 (d, JP,P ϭ 43.1 Hz, P-3). Ϫ IR (film): ν ϭ
˜
4.9 Hz, C(CH3)3], 30.9 [dd, JC,P ϭ 9.4/4.0 Hz, C(CH3)3], 33.6 [d,
2930, 2842, 2200 (PϪH), 1450, 1380, 1350, 1208, 1103, 1055 cmϪ1
.
2JC,P ϭ 6.3 Hz, C(CH3)3], 36.7 (d, JC,P ϭ 23.2 Hz, C2, H coupl.:
1
1
1JC,H ϭ 135.7 Hz), 40.9 [dd, JC,P ϭ 7.2/5.4 Hz, C(CH3)3], 129.1
2
2,4-Di-tert-butyl-2-dibutylchlorostannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (16c): From 15c (900 mg, 2.96 mmol), 14c (696 mg,
2.96 mmol) and 8a (2000 mg, 20 mmol) to furnish 16c (ca. 85%).
2
4
117/119
(s, JC,
117,119
ϭ 62.8 Hz, o-C), 129.5 (s, JC
117/119
ϭ 11.7 Hz, p-C),
Sn
Sn
138.0 (s, 3JC,
Sn ϭ 35.0 Hz, m-C), 139.6 (d, 2JC,P ϭ 2.7 Hz, ipso-
C), 238.1 (dd, 1JC,P ϭ 53.0/39.5 Hz, C-4). Ϫ 31P{1H} NMR (C6D6):
Ϫ
1H NMR (C6D6): δ ϭ 0.8Ϫ1.9 (m, 36 H, Bu-H and tBu-H),
δ ϭ 2.8 (d, 2JP,P ϭ 45.8 Hz, 1JP, Sn ϭ 1060.5 Hz, 1JP,117Sn ϭ 1014.7
1
3
119
6.77 (dd, JH,P ϭ 166.5 Hz, JH,P ϭ 19.5 Hz, 1 H, PϪH). Ϫ
2
3
13C{1H} NMR (C6D6): δ ϭ 14.0 [s, Sn(CH2)3CH3], 20.3 (s,
117,119
Hz, P-1), 353.3 (d, JP,P ϭ 45.8 Hz, JP,
ϭ 167.9 Hz, P-3). Ϫ
Sn
119Sn{1H} NMR (C6D6): δ ϭ Ϫ157 (dd, 1J
ϭ 1056 Hz,
3
119Sn,P
SnCH2), 27.2 (s, CH2CH2), 28.8 (s, CH2CH2), 29.7 [br. d, JC,P
ϭ
3
3
119
J
Sn,P ϭ 177 Hz). Ϫ IR (KBr): ν˜ ϭ 3060, 2960, 1430, 1360, 1075,
10 Hz, C(CH3)3], 30.7 [br. d, JC,P ϭ 4.0 Hz, C(CH3)3], 37.1 [d,
1025, 1000, 730, 700 cmϪ1. Ϫ MS: m/z (%) ϭ 551 (3) [Mϩ], 351
2JC,P ϭ 7.2 Hz, C(CH3)3], 40.2 [d, JC,P ϭ 2.4 Hz, C(CH3)3], 43.2
2
(81) [SnPh3ϩ], 131 (100) [P2C5H9ϩ], 57 (20) [C4H9ϩ].
C28H34P2Sn (551.23): calcd. C 61.0, H 6.2; found C 61.3, H 6.2.
Ϫ
1
1
(br. d, JC,P ϭ 33.7 Hz, C-2), 227.6 (dd, JC,P ϭ 53.0/23.3 Hz, C-
4). Ϫ 31P{1H} NMR (C6D6): δ ϭ Ϫ5.3 (d, JP,P ϭ 43 Hz, P-1),
2
2
366.1 (d, JP,P ϭ 43 Hz, P-3). Ϫ IR (film): ν ϭ 2930, 2900, 2880,
˜
trans-2,4-(Diadamant-1-yl)-1-tributylstannyl-1,2-dihydro-1λ3,
3λ3-diphosphete (18c): From 10c (200 mg, 0.31 mmol) to furnish
18c (200 mg, 100%) as a yellow, non-distillable oil. Ϫ 1H NMR
(C6D6): δ ϭ 0.9Ϫ2.3 (m, 57 H, Ad-H and Bu-H), 2.65 (s, 1 H,
PϪCH). Ϫ 13C{1H} NMR (C6D6): δ ϭ 11.0 (s, SnϪCH2), 13.9 (s,
SnϪ[CH2]3ϪCH3), 27.8 (s, SnCH2CH2), 29.1 (s, C-c), 29.2 (s, C-c),
2210 (PϪH), 1450, 1380, 1370, 1349, 1209, 1104, 1070, 1015 cmϪ1
.
2,4,6,9-Tetra-tert-butyl-8-dibutylstanna-1,3,5,7-tetraphospha-
pentacyclo[4.3.0.02,5.03,9.04,7]nonane (17c): From 15c (900 mg, 2.96
mmol), 13c (696 mg, 2.96 mmol) and 8a (2000 mg, 20 mmol) to
furnish 17c (210 mg, 6%) as yellow crystals with m.p. 145°C. Ϫ 1H
3
2
NMR (C6D6): δ ϭ 0.87 (t, JH,H ϭ 7.2 Hz, 6 H, CH2ϪCH3), 1.08
30.0 (s, CH2CH3), 35.6 (d, JC,P ϭ 5.7 Hz, C-a), 36.9 (s, Cd), 37.1
(s, C-d), 38.5 (d, JC,P ϭ 22.9 Hz, C-2), 40.3 (dd, JC,P ϭ 8.6/4.8
1
3
(s, 9 H, tBu-H), 1.22Ϫ1.47 (m, 8 H, CH2ϪCH2), 1.27 (s, 18 H,
tBu-H), 1.5Ϫ1.61 (m, 4 H, CH2ϪCH2), 1.72 (s, 9 H, tBu-H). Ϫ
13C{1H} NMR (C6D6): δ ϭ Ϫ17.2 (m, C-2), 13.6 [s, Sn(CH2)3CH3],
18.7 (s, SnCH2), 22.7 (m, C-9), 26.0 [m, 2 ϫ C(CH3)3], 27.1 [m, 2
ϫ C(CH3)3], 27.7 (s, CH2CH2), 30.2 (s, CH2CH2), 34.4 [m, 2 ϫ
C(CH3)3], 35.1 [pt, 2JC,P ϭ 7.2 Hz, 2 ϫ C(CH3)3], 37.6 (pt, 1JC,P ϭ
13.5 Hz, C-4/C-6). Ϫ 31P{1H} NMR (C6D6): δ ϭ Ϫ72.1 (dt, 2JP,P ϭ
2
3
Hz, C-b), 42.9 (dd, JC,P ϭ 6.7/3.8 Hz, C-a), 43.2 (dd, JC,P ϭ 9.1/
4.3 Hz, C-b), 240.4 (dd, JC,P ϭ 50.6/40.1 Hz, C-4). Ϫ 31P{1H}
1
2
1
117,119Sn
NMR (C6D6): δ ϭ 0.3 (d, JP,P ϭ 44.0 Hz, JP,
ϭ 907.2 Hz,
2
3
117,119Sn
P-1), 340.1 (d, JP,P ϭ 44.0 Hz, JP,
ϭ 149 Hz, P-3). Ϫ IR
(film): ν˜ ϭ 2985, 2870, 2850, 1455, 1350, 1250, 1070, 875, 840 cmϪ1
.
Ϫ C34H58P2Sn (647.49): calcd. C 63.1, H 9.0; found C 62.0, H 8.9.
1
2
21.0/7.6 Hz, JP,Sn ϭ 743.9 Hz, 1 P, P-7), 183.8 (dt, JP,P ϭ 21.0/
3
2
trans-2,4-(Diadamant-1-yl)-1-triphenylstannyl-1,2-dihydro-1λ3,
3λ3-diphosphete (18d): From 10d (198 mg, 0.28 mmol) to furnish
18d (198 mg, 100%) as a yellow, crystalline solid with m.p. 165°C.
15.3 Hz, JP,Sn ϭ 109 Hz, 1 P, P-5), 221.4 (dd, JP,P ϭ 15.3/7.6 Hz,
2 P, P-1/P-3). Ϫ Sn NMR (C6D6): δ ϭ 328 (dd, J
119
1
119Sn,P
ϭ 784
3
119
Hz, J
ϭ 113 Hz). Ϫ IR (KBr): ν˜ ϭ 2925, 2890, 2830, 1450,
Sn,P
1
1372, 1343, 1213, 760, 734, 696, 670 cmϪ1. Ϫ MS; m/z (%): 634
(15) [Mϩ], 521 (31) [Mϩ Ϫ 2Bu ϩ H], 400 (14) [Cubaneϩ]. Ϫ
C28H54P4Sn (633.3): calcd. C 53.1, H 8.6; found C 53.2, H 8.4.
Ϫ H NMR (C6D6): δ ϭ 1.2Ϫ2.15 (m, 30 H, Ad-H), 2.43 (br., 1
H, PCϪH), 6.9Ϫ7.35 (m, 9 H, m-, p-C6H5), 7.5Ϫ7.8 (m, 6 H, o-
C6H5). Ϫ 13C{1H} NMR (C6D6): δ ϭ 28.89 (s, C-c), 28.92 (s, C-
2
c), 35.6 (d, JC,P ϭ 5.6 Hz, C-a), 36.5 (s, C-d), 36.9, (s, C-d), 39.1
Thermolysis of 10a؊d. Ϫ General Procedure: The 1,2-dihydro-
1,3-diphosphete 10 was dissolved in toluene (5 ml) and heated at
90°C for 6 h. Removal of the solvent yielded the 1-stannyl-substi-
tuted 1,2-dihydro-1,3-diphosphetes 18.
1
3
(d, JC,P ϭ 24.1 Hz, C-2), 40.1 (dd, JC,P ϭ 8.0/4.1 Hz, C-b), 43.1
2
2
(dd, JC,P ϭ 8.8/4.0 Hz, C-b), 43.4 (dd, JC,P ϭ 6.8/3.5 Hz, C-a),
4
117/119Sn
129.0 (s, o-C), 129.4 (s, JC,
ϭ 11.2 Hz, p-C), 137.7 (s,
3
117/119
JC,
Sn ϭ 34.5 Hz, m-C), 139.9 (d, 2JC,P ϭ 2.4 Hz, ipso-C), 238.4
trans-2,4-Di-tert-butyl-1-tributylstannyl-1,2-dihydro-1λ3,3λ3- (dd, JC,P ϭ 51.4/39.4 Hz, C-4). Ϫ 31P{1H} NMR (C6D6): δ ϭ
1
2
1
117,119Sn
ϭ 1050.5 Hz, P-1), 349.4 (d,
diphosphete (18a): From 10a (413 mg, 0.84 mmol) to furnish 18a
Ϫ5.0 (d, JP,P ϭ 45.8 Hz, JP,
3
(413 mg, 100%) as a yellow oil with b.p. 170°C/5 ϫ 10Ϫ3 mbar. Ϫ 2JP,P ϭ 45.8 Hz, JP,
ϭ 175 Hz, P-3). Ϫ 119Sn{1H} NMR
117,119Sn
1
1H NMR (C6D6): δ ϭ 0.9Ϫ1.9 (m, 45 H, Bu-H and tBu-H), 2.05 (C6D6): δ ϭ Ϫ159 (dd, J
ϭ 1099 Hz, J
ϭ 177 Hz). Ϫ
3
119
119
Sn,P
Sn,P
2
(s, 1 H, PCϪH). Ϫ 13C{1H} NMR (C6D6): δ ϭ 10.8 (d, JC,P
ϭ
IR (KBr): ν˜ ϭ 3030, 2870, 2820, 1460, 1430, 1410, 1330, 1300,
Eur. J. Inorg. Chem. 1998, 227Ϫ235
233

M. Schmitz, R. Göller, U. Bergsträßer, S. Leininger, M. Regitz
FULL PAPER
1250, 1090, 985, 715, 685 cmϪ1. Ϫ MS; m/z (%): 708 (2) [Mϩ], 700
µ-(2,4-Di-tert-butyl-2-tributylstannyl-1,2-dihydro-η1-1λ3,η1-3λ3-
(3) [(SnPh3)2ϩ], 357 (15) [Mϩ Ϫ SnPh3], 351 (100) [SnPh3ϩ], 135 diphosphete)bis(tetracarbonyliron) (21a): From enneacarbonyldii-
(73) [Adϩ]. Ϫ C40H46P2Sn (707.5): calcd. C 67.9, H 6.6; found C ron (1.5 g, 4 mmol) and 1,2-dihydro-1,3-diphosphete 10a (920 mg,
67.7, H 6.7.
1.87 mmol) to furnish 21a (420 g, 27%) as a red-brown solid with
m.p. 184°C. Ϫ H NMR (CD2Cl2): δ ϭ 0.95 (t, JH,H ϭ 7.21 Hz,
9 H, CH2CH3), 1.21Ϫ1.66 (m, 18 H, CH2), 1.44 (s, 9 H, tBu-H),
1
3
Complexations
Tetrahydrofuran.
of
Ϫ
10a,b
General Procedure:
with
Pentacarbonyltungsten·
solution of
A
1
3
1.45 (s, 9 H, tBu-H), 7.20 (dd, JH,P ϭ 307.25 Hz, JH,P ϭ 30.52
pentacarbonyltungsten·THF was prepared by irradiation of a solu-
tion of hexacarbonyltungsten in THF (HPK, 125 W, Phillips) for
35 min. To this solution was added 10 in THF (10 ml) and the
mixture was stirred at room temperature for 24 h. The solvent was
then removed under vacuum and excess hexacarbonyltungsten was
sublimed at 40°C under vacuum. The residue was taken up in pen-
tane and yielded compounds 19, 20 on crystallization at Ϫ20°C.
Hz, 1 H, P-H). Ϫ 13C{1H} NMR (C6D6): δ ϭ 13.7 (s, SnϪCH2),
15.2 (s, SnϪ[CH2]3ϪCH3), 27.8 (s, JC,
2
117/119Sn
ϭ 71.5 Hz,
ϭ 17.8 Hz, CH2CH3), 30.6 [dd,
3
117/119Sn
SnCH2CH2), 29.8 (s, JC,
3JC,P ϭ 11.2/10.4 Hz, C(CH3)3], 31.1 [s, C(CH3)3], 38.2 [s, C(CH3)3],
39.8 [s, C(CH3)3], 61.9 (d, 1JC,P ϭ 14.8 Hz, C-2), 195.1 (pt, 1JC,P ϭ
2
2
14.4 Hz, C-4), 214.6 (d, JC,P ϭ 11.2 Hz, CO), 217.3 (d, JC,P
ϭ
10.4 Hz, CO). Ϫ 31P{1H} NMR (C6D6): δ ϭ 48 (d, JP,P ϭ 27 Hz,
P-1), 315 (d, 2JP,P ϭ 26 Hz, P-3). Ϫ IR (pentane): ν˜ ϭ 2986Ϫ2843,
2068 (P-H), 2054 (CO), 1971 (CO), 1472, 1453, 1362, 1261, 1022,
2
(2,4-Di-tert-butyl-2-triphenylstannyl-1,2-dihydro-η1-1λ3,3λ3-
diphosphete)pentacarbonyltungsten (19): From hexacarbonyltung-
sten (1.75 g, 5 mmol) and 1,2-dihydro-1,3-diphosphete 10b (2.05 g,
3.72 mmol) to furnish 19 (1.46 g, 45%) as a yellow-orange, crystal-
line powder with m.p. 153.2°C (dec.). Ϫ 1H NMR (C6D6): δ ϭ
1.18 (s, 9 H, tBu-H), 1.69 (s, 9 H, tBu-H), 7.39Ϫ7.45 (m, 9 H, m-,
907, 730 cmϪ1. Ϫ MS; m/z (%): 828 (0.2) [Mϩ], 660 (1) [Mϩ
Ϫ
Fe(CO)4], 492 (16) [Mϩ Ϫ 2 Fe(CO)4], 291 (70) [SnBu3ϩ], 235 (96)
[HSnBu2ϩ], 179 (100) [H2SnBuϩ], 57 (33) [C4H9ϩ],
Ϫ
C30H46Fe2O8P2Sn (827.02): calcd. C 43.57, H 5.61; found C 43.13,
H 5.61.
1
p-C6H5), 7.9Ϫ8.0 (m, 6 H, o-C6H5), 9.08 (dd, JH,P ϭ 280 Hz,
3JH,P ϭ 13.8 Hz, 1 H, P-H). Ϫ 13C{1H} NMR (C6D6): δ ϭ 29.5
µ-(2,4-Di-tert-butyl-2-triphenylstannyl-1,2-dihydro-η1-1λ3,η1-3λ3-
diphosphete)bis(tetracarbonyliron) (21b): From enneacarbonyldii-
ron (400 mg, 1.1 mmol) and 1,2-dihydro-1,3-diphosphete 10b (200
mg, 0.36 mmol) to furnish 21b (220 mg, 69%) as a red-brown solid
3
3
[d, JC,P ϭ 5.0 Hz, C(CH3)3], 31.3 [d, JC,P ϭ 7.0 Hz, C(CH3)3],
37.5 [s, C(CH3)3], 39.9 [s, C(CH3)3], 45.6 (dd, 1JC,P ϭ 40/13 Hz, C-
2), 129.1 (s, o-C), 129.7 (s, p-C), 137.8 (s, m-C), 140.1 (s, ipso-C),
2
2
1
198.1 (d, JC,P ϭ 6.4 Hz, COequatorial), 198.7 (d, JC,P ϭ 18.5 Hz,
with m.p. 124°C. Ϫ H NMR (CD2Cl2): δ ϭ 1.05 (s, 9 H, tBu-H),
COaxial), 209.5 (dd, JC,P ϭ 52/11 Hz, C-4). Ϫ 31P{1H} NMR
1
1.60 (s, 9 H, tBu-H), 7.39Ϫ7.79 (m, 15 H, C6H5), 7.67 (dd, 1JH,P ϭ
1
3
308.18 Hz, JH,P ϭ 28.82 Hz, 1 H, PϪH). Ϫ 13C{1H} NMR
(C6D6): δ ϭ 15.3 (s, JP,W ϭ 209 Hz, P-1), 399.2 (s, P-3). Ϫ
119Sn{1H} NMR (C6D6): δ ϭ Ϫ98.6 (m). Ϫ IR (KBr): ν˜ ϭ 3020,
2920, 2200 (PϪH), 2020 (CO), 1960 (CO), 1900 (CO), 1450, 1400,
1050, 820 cmϪ1. Ϫ MS: m/z (%) ϭ 875 (24) [Mϩ], 797 (100) [Mϩ
(C6D6): δ ϭ 29.7 [dd, 3JC,P ϭ 11.2 Hz, C(CH3)3], 31.7 [s, C(CH3)3],
1
38.5 [s, C(CH3)3], 39.5 [s, C(CH3)3], 65.3 (dd, JC,P ϭ 20.5/5.6 Hz,
2
117/119Sn
C-2), 129.3 (s, JC,
ϭ 53.0 Hz, o-C), 130.1 (s, p-C), 137.9 (s,
Ph], 553 (24) [Mϩ W(CO)5], 351 (96) [SnPh3ϩ].
Ϫ Ϫ
3
1
Ϫ
117/119
JC,
ϭ 37.0 Hz, m-C), 139.8 (s, ipso-C), 196.3 (pt, JC,P ϭ 15
Sn
2
2
C33H34O5P2SnW (875.12): calcd. C 45.3, H 3.9; found C 45.3, H
4.0.
Hz, C-4), 213.8 (d, JC,P ϭ 10.4 Hz, CO), 216.6 (d, JC,P ϭ 10.4
Hz, CO). Ϫ 31P{1H} NMR (C6D6): δ ϭ 47 (d, JP,P ϭ 34 Hz, P-
2
2
1), 313 (d, JP,P ϭ 33 Hz, P-3). Ϫ IR (KBr): ν˜ ϭ 3449, 2959, 2236
µ-(2,4-Di-tert-butyl-2-tributylstannyl-1,2-dihydro-η1-1λ3,η1-3λ3-
diphosphete)bis(pentacarbonyltungsten) (20): From hexacarbo-
nyltungsten (600 mg, 1.7 mmol) and 1,2-dihydro-1,3-diphosphete
10a (260 mg, 0.53 mmol) to furnish 20 (360 mg, 60%) as a yellow
powder with m.p. 118°C (dec.). Ϫ 1H NMR (C6D6): δ ϭ 0.91Ϫ1.67
(PϪH), 2072 (CO), 2057 (CO), 2007 (CO), 1981 (CO), 1945 (CO),
1450, 1428, 1360, 1211, 843 cmϪ1. Ϫ MS; m/z (%): 887 (0.2) [Mϩ
Ϫ H], 748 (1) [Mϩ Ϫ 5 CO], 351 (100) [SnPh3ϩ], 169 (51) [HFe(CO)
ϩ], 57 (55) [C4H9ϩ].
4
3
2,4-Di-tert-butyl-1-iodo-2-triphenylstannyl-1,2-dihydro-1λ3,3λ3-
diphosphete (22): A solution of iodine (280 mg, 1.1 mmol) in diethyl
ether was added dropwise to a suspension of 1,2-dihydro-1,3-di-
phosphete 10b (600 mg, 1.1 mmol) in diethyl ether (5 ml). The
reaction mixture was stirred 15 min at room temperature and then
the solvent and all volatile compounds were removed under
vacuum to furnish 22 as a yellow, non-distillable oil. Yield: about
(m, 36 H, CH2 and tBu-H), 0.97 (t, JH,H ϭ 7.24 Hz, 9 H,
1
3
CH2CH3), 7.71 (dd, JH,P ϭ 295.09 Hz, JH,P ϭ 31.81 Hz, 1 H,
P-H). Ϫ 13C{1H} NMR (C6D6): δ ϭ 13.6 (s, SnϪCH2), 15.1 (s,
117/119
SnϪ[CH2]3ϪCH3), 27.7 (s, 2JC,
Sn ϭ 69.1/72.3 Hz, SnCH2CH2),
3
3
117/119Sn
29.8 (s, JC,
ϭ 18.5 Hz, CH2CH3), 31.4 [d, JC,P ϭ 4.8 Hz,
C(CH3)3], 31.5 [d, 3JC,P ϭ 5.6 Hz, C(CH3)3], 36.9 [s, C(CH3)3], 39.5
1
1
[s, C(CH3)3], 51.9 (dd, JC,P ϭ 16/8 Hz, C-2), 194.9 (dd, JC,P
ϭ
2
1
39.8/7.7 Hz, C-4), 195.8 (d, JC,P ϭ 7.2 Hz, COequatorial), 196.5 (d,
90%. Ϫ H NMR (C6D6): δ ϭ 1.05 (s, 9 H, tBu-H), 1.22 (s, 9 H,
2JC,,P ϭ 31.3 Hz, COaxial), 197.9 (d, JC,P ϭ 5.6 Hz, COequatorial),
2
tBu-H), 7.0Ϫ7.29 (m, 9 H, m-, p-C6H5), 7.87Ϫ8.12 (m, 6 H, o-
2
198.5 (d, JC,P ϭ 28.9 Hz, COaxial). Ϫ 31P{1H} NMR (C6D6): δ ϭ
3
C6H5). Ϫ 13C{1H} NMR (C6D6): δ ϭ 30.2 [d, JC,P ϭ 4.5 Hz,
2
1
2
C(CH3)3], 30.6 [dd, 3JC,P ϭ 11.7/3.6 Hz, C(CH3)3], 38.8 [d, 2JC,P ϭ
6 (d, JP,P ϭ 26 Hz, JP,W ϭ 222 Hz, P-1), 294 (d, JP,P ϭ 26 Hz,
1JP,W ϭ 244 Hz, P-3). Ϫ IR (pentane): ν˜ ϭ 2972, 2929, 2079
2
8.1 Hz, C(CH3)3], 41.5 [dd, JC,P ϭ 7.2/2.7 Hz, C(CH3)3], 58.1 (pt,
(PϪH), 2070 (CO), 1982 (CO), 1964 (CO), 1464, 1378, 893 cmϪ1
.
4
1JC,P ϭ 42.6 Hz, C-2), 130.4 (s, JC,
ϭ 13.5 Hz, p-C), 136.6
117/119Sn
Ϫ MS; m/z (%): 1138 (2) [Mϩ], 847 (39) [Mϩ Ϫ SnBu3], 813 (17)
(s, 2JC,
Sn ϭ 48.5 Hz, o-C), 138.8 (s, 3JC,
Sn ϭ 36.8 Hz, m-C),
117/119
117/119
[Mϩ Ϫ W(CO)5 Ϫ H], 679 (53) [Mϩ Ϫ SnBu3 Ϫ 6 CO], 291 (100)
142.6 (s, ipso-C), 230.3 (pt, 1JC,P ϭ 56.6 Hz, C-4). Ϫ 31P{1H} NMR
[SnBu3ϩ], 235 (72) [HSnBu2ϩ], 57 (32) [C4H9ϩ].
Ϫ
2
2
(C6D6): δ ϭ 5.5 (d, JP,P ϭ 126.4 Hz, P-1), 324.9 (d, JP,P ϭ 126.4
Hz, P-3). Ϫ IR (film): ν˜ ϭ 3035, 2930, 1460, 1420, 1355, 1065,
1015, 990, 720, 690 cmϪ1. Ϫ MS; m/z (%): 677 (10) [Mϩ], 351 (71)
[SnPh3ϩ], 77 (51) [Phϩ], 57 (21) [C4H9ϩ].
C32H46O10P2SnW2 (1139.04): calcd. C 33.74, H 4.07; found C
32.86, H 3.90.
Complexations of 10a,b with Enneacarbonyldiiron. Ϫ General
Procedure: To a solution of 10 in pentane (10 ml) was added ennea-
carbonyldiiron and the mixture stirred at room temperature for 24 graphite monochromator, Mo-Kα (λ ϭ 0.71073 A), structure solu-
h. The solution was then filtered through Celite and compounds
21 were crystallized from pentane at Ϫ78°C.
X-ray Structural Analysis of 18d[33]: Siemens P-4 diffractometer,
˚
tion by direct methods (SHELXTL-PLUS[34]) and structure refine-
ment by SHELXL-93[35]. Semi-empirical absorption correction by
234
Eur. J. Inorg. Chem. 1998, 227Ϫ235

Organophosphorus Compounds, 125
FULL PAPER
hydro-1,3-diphosphete in temperature-dependent 31P-NMR
use of Ψ scans. Hydrogen atoms were placed in geometrically calcu-
measurements, see also ref.[8]
.
lated positions (dCϪH ϭ 0.960 A). C40H46P2Sn; M ϭ 707.4 g.molϪ1
;
˚
[17]
[18]
[19]
G. Bähr, S. Pawlenko in Houben-Weyl: Methoden der Or-
ganischen Chemie, Metallorganische Verbindungen, Vol. 13/6
Germanium, Zinn, 4th ed., Thieme, Stuttgart, 1978, p. 239.
T. Wettling, J. Schneider, O. Wagner, C. G. Kreiter, M. Regitz,
Angew. Chem. 1989, 101, 1035Ϫ1037; Angew. Chem. Int. Ed.
Engl. 1989, 28, 1013Ϫ1015.
R. Gleiter, K. H. Pfeifer, M. Baudler, G. Scholz, T. Wettling,
M. Regitz, Chem. Ber. 1990, 123, 757Ϫ760.
W. McFarlane, N. H. Rees, Polyhedron 1989, 8, 2047Ϫ2050.
J. P. Albrand, D. Gagnaire, J. B. Robert, J. Chem. Soc., Chem.
Commun. 1968, 1469Ϫ1470.
monoclinic; space group C2/c; a ϭ 33.813(7), b ϭ 9.565(2), c ϭ
21.797(4) A, β ϭ 101.33(3)°, V ϭ 6912(2) A3; Z ϭ 8; Dcalcd.
ϭ
˚
˚
1.360 Mg/m3; µ ϭ 8.59 cmϪ1; crystal size 0.30 ϫ 0.25 ϫ 0.20 mm;
ω scan: 1.23° Յ Θ Յ 26.00°. 7998 reflections collected, 6750 inde-
pendent reflections (Rint. ϭ 0.0254); max./min. transmission: 0.880/
0.761; 392 parameters; w-1 ϭ [σ2(Fo2) ϩ (0.0466P)2 ϩ 8.3105P] and
[20]
[21]
2
P ϭ [(Fo2)ϩ2Fc ]/3; R ϭ 0.0386, Rw ϭ 0.0905 for 6750 reflections
with I > 2σ(I) and R ϭ 0.0651, Rw ϭ 0.1039 for all data; residual
electron density 483 e.nmϪ3 and Ϫ433 e.nmϪ3, GOF (on F2) ϭ
1.007.
[22]
R. Appel: “Phosphaalkenes, Phosphacarbaoligoenes and Phos-
phaallenes” in Multiple Bonds and Low Coordination in Phos-
phorus Chemistry (Eds.: M. Regitz, O. J. Scherer), 1st ed., Thi-
eme, Stuttgart 1990, p. 160.
[23]
[24]
J. Emsley, D. Hall, The Chemistry of Phosphorus, Harper & Row
Ltd., London 1976, p. 177Ϫ207.
Ƞ
Dedicated to Professor Manfred Weidenbruch on the occasion
O. Stelzer, Topics in Phosphorus Chemistry, Wiley & Sons, New
York, 1977, vol. 9, p. 1Ϫ229.
of his 60th birthday.
[1]
A. Nachbauer, U. Bergsträßer, S. Leininger, M. Regitz, Syn-
[25] [25a]
E. O. Fischer, L. Knauss, R. L. Keiter, J. G. Verkade, J.
thesis 1997, in press.
Organomet. Chem. 1972, 37, C7ϪC10. Ϫ [25b] H. C. E. Mc Far-
lane, W. Mc Farlane, D. S. Rycroft, J. Chem. Soc. Dalton Trans.
1976, 1616Ϫ1622.
[2]
G. J. M. van der Kerk, J. G. A. Luijten, J. G. Noltes, Chem.
Ind. 1956, 352.
[3]
G. J. M. van der Kerk, J. G. A. Luijten, J. G. Noltes, J. Appl.
See ref.[17], p. 257 and references cited therein.
A. E. Finholt, A. C. Bord Jr., K. E. Wilzbach, H. E. Schles-
inger, J. Am. Chem. Soc. 1947, 69, 2692Ϫ2696.
A. K. Sawyer, J. E. Brown, G. S. May, J. Organomet. Chem.
1968, 11, 192Ϫ194.
[26]
[27]
Chem. 1959, 9, 106Ϫ113.
[4] [4a]
J. G. Noltes, G. J. M. van der Kerk, Chimia 1962, 16,
122Ϫ127. Ϫ [4b] J. G. Noltes, G. J. M. van der Kerk, Recl. Trav.
Chim. Pays-Bas 1962, 81, 41Ϫ48.
[28]
[29]
[30]
[31]
[32]
[33]
[5]
A. K. Sawyer, H. G. Kuivila, Chem. Ind. 1961, 260.
G. J. M. van der Kerk, J. G. Noltes, J. G. A. Luijten, J. Appl.
Chem. 1957, 7, 366Ϫ369.
[6]
W. P. Neumann, J. Pedain, Tetrahedron Lett. 1964, 2461Ϫ2465.
[7]
M. Schmitz, R. Göller, M. Regitz, Synthesis 1997, 455Ϫ460.
K. A. Kocheshkov, Ber. Dtsch. Chem. Ges. 1933, 66,
1661Ϫ1665.
[8]
R. Appel, V. Barth, F. Knoch, Chem. Ber. 1983, 116, 938Ϫ950.
[9]
B. Breit, M. Regitz, Chem. Ber. 1993, 126, 1945Ϫ1950.
W. Rösch, U. Hees, M. Regitz, Chem. Ber. 1987, 120,
1645Ϫ1652.
[10]
S. Lochschmidt, A. Schmidpeter, Phosphorus Sulfur 1988, 29,
73Ϫ109.
T. Allspach, M. Regitz, G. Becker, W. Becker, Synthesis 1986,
31Ϫ36.
[11] [11a]
G. Becker, W. Becker, R. Knebl, H. Schmidt, M. Milden-
brand, M. Westerhausen, Phosphorus Sulfur 1987, 30, 349Ϫ352.
Further details of the crystal structure determination are avail-
able on request from the Fachinformationszentrum Karlsruhe,
Gesellschaft für wissenschaftlich-technische Information mbH,
D-76344 Eggenstein-Leopoldshafen, on quoting the depository
number CSD-407748, the names of the authors, and the jour-
nal citation.
[11b]
Ϫ
R. Knebl, Ph.D. Thesis, University of Stuttgart, 1988.
[12]
[13]
R. Schneider, Ph.D. Thesis, University of Kaiserslautern, 1991.
K. Karaghiosoff in Multiple Bonds and Low Coordination in
Phosphorus Chemistry (Eds.: M. Regitz, O. J. Scherer), 1st ed.,
Thieme, Stuttgart 1990, p. 463ff.
[14]
[15]
[16]
[34]
[35]
A. P. Tupciauskas, N. M. Sergeev, Yu. A. Ustynyk, Org. Magn.
Resonance, 1971, 3, 655Ϫ659.
SHELXTL-PLUS, Siemens Analytical X.-ray Instruments, Ma-
dison, Wisconsin, USA 1991.
W. McFarlane, J. C. Maire, M. Delmas, J. Chem. Soc., Dalton
Trans. 1972, 1862Ϫ1865.
G. M. Sheldrick, SHELXL-93, a program for structure refine-
ment, Göttingen, Germany, 1993.
Appel and coworkers reported only one isomer of a 1,2-di-
[97215]
Eur. J. Inorg. Chem. 1998, 227Ϫ235
235