Synthesis and reactions of (1,1′-bi-1H-phosphirene)iron complexes - Crystal structure of a bridged (1-phosphaallyl-1H-phosphirene)diiron(Fe-Fe) complex

Article abstract of DOI:10.1002/1099-0682(200108)2001:8<2067::AID-EJIC2067>3.0.CO;2-R

The reactions of 1-chloro-1H-phosphirenes 5 with disodium tetracarbonlyferrate lead to the selective formation of the mono complexed bi-1H-phosphirenes 7, which are converted into the doubly complexed species 9 upon treatment with diiron nonacarbonyl. Photochemical opening of one of the two three-membered ring systems in 9 furnishes the bridged complexes 10 containing phosphirene and phosphaallyl units together with an iron-iron σ-bond.

Full text of DOI:10.1002/1099-0682(200108)2001:8<2067::AID-EJIC2067>3.0.CO;2-R

FULL PAPER
Synthesis and Reactions of (1,1Ј-Bi-1H-phosphirene)iron Complexes ؊ Crystal
Structure of a Bridged (1-Phosphaallyl-1H-phosphirene)diiron(Fe؊Fe)
Complex[‡]
Jürgen Simon,[a] Guido J. Reiß,[a] Uwe Bergsträßer,[a] Heinrich Heydt,*[a] and
Manfred Regitz*[a]
Keywords: Iron / Phosphorus heterocycles / P ligands / Valence isomerization / Twinning
The reactions of 1-chloro-1H-phosphirenes 5 with disodium
iron nonacarbonyl. Photochemical opening of one of the two
tetracarbonlyferrate lead to the selective formation of the
three-membered ring systems in 9 furnishes the bridged
mono complexed bi-1H-phosphirenes 7, which are converted complexes 10 containing phosphirene and phosphaallyl units
into the doubly complexed species 9 upon treatment with di-
together with an iron-iron σ-bond.
Results and Discussion
Introduction
Since the 1960’s investigations on the synthesis and react-
ivity of phosphinines and their valence isomers have played
a significant role in the development of the chemistry of
low-coordinated phosphorus compounds.[2Ϫ5] In contrast,
the only known representatives of diphosphinines are the
1,3[6] and 1,4 derivatives[7] 1 and 2 (Scheme 1). Recently,
an access to valence isomers of the 1,3-diphospha-Dewar-
benzene 3 and diphosphabenzvalene 4 types was established
using specific trapping reactions of a short-lived 1,3-diphos-
phacyclobutadiene with suitably substituted alkynes.[8] 1,3-
Diphosphinines 1 are also able to undergo a valence iso-
merization to the Dewar isomers on prolonged heating.[6c]
Synthesis of the (1,1Ј-Bi-1H-phosphirene)iron Complexes 7a
and 7b
In the reactions of the 1-chloro-1H-phosphirenes 5 with
disodium tetracarbonylferrate, the mono η1 complexed
1,1Ј-bi-1H-phosphirenes 7a and 7b (58 and 60%) are
formed highly selectively (Scheme 2), instead of the ex-
pected η3:3-(bisphosphirenylium)dicarbonyliron complexes
6.
Scheme 1
In the present report, we described the synthesis of the
iron complexed 1,1Ј-bi-1H-phosphirenes 7 and 9 as a fur-
ther, previously unknown class of valence isomers of the
diphosphinines.[9] Very recently, the corresponding 1,1Ј-bisi-
lacyclopropenes, the valence isomers of 1,4-disilabenzenes,
have also been synthesized.[10]
Scheme 2
Elemental analysis and mass spectroscopic data unequi-
vocally demonstrate that the complexes 7a and 7b are 2:1
adducts of the 1-chloro-1H-phosphirenes 5a and 5b with
Collman’s reagent, formed under concomitant loss of two
molecules of sodium chloride.
[‡]
Organophosphorus Compounds, 154. Ϫ Part 153: Ref.[1]
[a]
Fachbereich Chemie der Universität Kaiserslautern,
Erwin-Schrödinger-Straße, 67663 Kaiserslautern, Germany
Fax: (internat.) ϩ49 (0)631 205 3921
E-mail: heydt@chemie.uni-kl.de
Mixtures of two diastereomers that cannot be separated
by column chromatography are obtained. One diastere-
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/0808Ϫ2067 $ 17.50ϩ.50/0
2067

J. Simon, G. J. Reiß, U. Bergsträßer, H. Heydt, M. Regitz
FULL PAPER
omer, however, can be enriched up to a ratio of 8:1 (7a) Further Complexation of (1,1Ј-Bi-1H-phosphirene)iron
1
or 4:1 (7b) (as determined by H NMR spectroscopy) by Complexes 7a and 7b with Diironnonacarbonyl To Afford
crystallization. The NMR spectroscopic data provide dia- (1,1Ј-Bi-1H-phosphirene)diiron Complexes 9a and 9b
gnostic information for the structure elucidation, as discus-
sed below for the example of 7a (major diastereomer; R ϭ
tBu).
The additional complexation of the free phosphorus
atom provides a possibility to improve the crystallization
properties of the novel diphosphinine valence isomers 7.
Reactions of 7 with a slight excess of diiron nonacarbonyl
proceed selectively to afford the (1,1Ј-bi-1H-phosphirene)-
diiron complexes 9 carrying two tetracarbonyliron frag-
ments (Scheme 4). After workup by column chromato-
graphy and subsequent recrystallization from n-pentane the
binuclear complexes 9a and 9b are obtained in good yields
(63% and 54%, respectively) in the form of yellow-orange
crystals.
The formation of this product is demonstrated by its 31P
1
NMR spectrum, which reveals a significant, large JP,P
coupling constant of 427.3 Hz. The signal at δ ϭ Ϫ88.1 is
assigned to the iron complexed phosphorus atom P-1 by
comparison with the published values for iron complexed
1H-phosphirenes[11], while the signal at higher field (δ ϭ
Ϫ134.2) originates from the non-complexed phosphirene
unit.
A conspicuous feature of the 13C NMR spectrum of 7a
is a drastic reduction of the intracyclic carbon/phosphorus
coupling constants in the complexed three-membered ring
(1JC,P ϭ 22.0 and 27.1 Hz) in comparison with those of
the non-complexed three-membered ring (1JC,P ϭ 50.8 and
57.7 Hz). This is a generally observed phenomenon on go-
ing from three- to four-coordinated 1H-phosphirenes.[12]
The chemical shifts of the alkyl- and aryl-substituted ring
carbon atoms are also in agreement with literature data.[13]
The resonance signals at lower field (δ ϭ 140.5 and 138.5)
are attributed to the alkyl-substituted carbon atoms C-3
and C-3Ј while the phenyl-substituted C atoms C-2 and C-
2Ј give rise to the signals at markedly higher field (δ ϭ 124.8
and 120.3).
Scheme 4
The formation of 7a and 7b must proceed through a
multi-step sequence, although 31P NMR monitoring of the
reaction mixture did not provide any indications for the ex-
istence of intermediates (Scheme 3).
Elemental analysis and mass spectroscopic data unequi-
vocally confirm the presence of two Fe(CO)4 fragments in
9a and 9b. The NMR spectroscopic data of these complexes
are highly simplified, and discussed for the example of the
main diastereomer 9a.
The magnetically equivalent phosphorus atoms P-1 and
P-1Ј in 9a give rise to a singlet signal in the 31P NMR spec-
trum at δ ϭ Ϫ69.3. In comparison to the spectrum of 7a
the additional complexation results in a pronounced deshi-
elding by 64.9 ppm of the 31P NMR signals of the formerly
non-coordinated phosphorus.
The 13C NMR spectrum of 9a reflects the double com-
plexation by the appearance of pseudo-triplet signals for the
carbonyl and ring carbon atoms. Furthermore, the intra-
cyclic phosphorus-carbon coupling constants of the 1H-
phosphirene unit that was not complexed in 7a are, as ex-
pected, drastically reduced as a result of the complexation
with the second tetracarbonyliron fragment. In analogy
with compound 7, the signals for the ring carbon atoms
seen at lower field are assigned to the alkyl-substituted car-
bon atoms C-3 and C-3Ј (δ ϭ 142.2). Similar to the 31P
Scheme 3
A plausible mechanism involves the substitution of the NMR spectroscopic data of 9a and 9b, the 13C NMR sig-
chlorine atom in 5 by an anionic tetracarbonyliron frag- nals of the ring carbon atoms also experience a clear shift
ment to afford the anionic 1H-phosphirene complex 8. This to lower field as a result of the additional complexation.
complex then undergoes an immediate nucleophilic substi-
Final confirmation of the structure of the iron complexed
tution with a further molecule of 5 to afford the mono com- 1,1Ј-bi-1H-phosphirene 9a was obtained by X-ray crystallo-
plexed 1,1Ј-bi-1H-phosphirenes 7.
graphy.[9]
2068
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073

Synthesis and Reactions of (1,1Ј-Bi-1H-phosphirene)iron Complexes
FULL PAPER
The carbon atoms C-2Ј and C-3Јof the 1-phosphaallyl
element give rise to signals at δ ϭ 191.2 and 153.9. Since
the signal at lower field is split into a double doublet it is
assigned to the C-2Ј atom directly bonded to phosphorus.
The extremely low-field position of this signal is also char-
acteristic for a PϭC double bond system. The bridging car-
bon atom C-3Ј of 10a, on the other hand, gives a signal at
appreciably higher field. A comparison of the chemical shift
of this carbon atom (C-3Ј; δ ϭ 153.9) with the published
values for bridged allyl complexes[16] provides further sup-
port for this structure. The signals of the ring carbon atoms
C-2 and C-3 are found at δ ϭ 150.6 (C-3) and δ ϭ 124.6
(C-2) in the region typical for 1H-phosphirenes with this
substitution pattern. The chemical shifts have been assigned
analogously to those for compounds 7 and 9. Although the
13C{1H} NMR signals of the phenyl substituents cannot be
assigned individually, this is possible for the alkyl substitu-
ents. As expected, two sets of signals are observed for the
two tert-butyl groups, with one of the signal sets being
markedly shifted to lower field. By comparison with the
values for other allyl complexes,[15] the signals at lower field
are attributed to the alkyl substituents at C-2Ј.
Photolyses of the (1,1Ј-Bi-1H-phosphirene)diiron Complexes
9a and 9b To Give the (1-Phosphaallyl-1H-phosphirene)-
diiron(Fe؊Fe) Complexes 10a and 10b
Previously, only a single example of a photochemically
induced rig opening reaction of a complexed 1H-phosphir-
ene was known.[14] When a solution of the doubly com-
plexed 1,1Ј-bi-1H-phosphirenes 9a or 9b in C6D6 is irradi-
ated in an NMR tube using a 125 W high-pressure mercury
lamp, 31P NMR monitoring of the mixture reveals a rela-
tively unselective reaction sequence (Scheme 5). After
workup by column chromatography and subsequent recrys-
tallization from n-pentane/diethyl ether, the pure com-
pounds 10a or 10b are isolated only in low yields (5 and
6%, respectively).
This low-field signal shift of the substituents of the phos-
1
phaallyl unit is also observed in the H NMR spectrum of
10a. Thus, the tert-butyl group at C-2Ј gives rise to a signal
at δ ϭ 1.42, while the alkyl substituent of the phosphirene
ring produces a signal at δ ϭ 1.16. The signals of the pro-
tons of the phenyl groups overlap, resulting in the observa-
Scheme 5
Elemental analysis and mass spectroscopic data unam- tion of only a multiplet in the typical aromatic proton re-
biguously demonstrate the cleavage of two carbonyl groups gion.
from 9a and 9b. The NMR spectroscopic data also provide
The structure of 10a was finally and irrevocably con-
diagnostic information on the constitutions of compounds firmed by X-ray crystallography (Figure 1).
10a and 10b.
The 31P NMR spectra, discussed here for the example of
10a, contains two doublets at δ ϭ Ϫ1.6 and Ϫ70.4. Of
these, the signal at higher field is only shifted slightly in
comparison to that of the starting compound 9a, thus con-
firming the retention of one of the two 1H-phosphirene un-
its. On the other hand, the low-field shift of the other doub-
let indicates that the second three-membered ring unit has
been opened. This signal can be assigned to a (1-phosphaal-
lyl)iron complex by comparison with published values for
structural increments of this type.[15]
The 13C{1H} NMR spectrum of 10a is in agreement with
the proposed structure, and contains 8 different signals in
addition to those of the aryl and alkyl substituents. Al-
though only one doublet at δ ϭ 212.4 with a coupling con-
stant of 6.8 Hz is observed for one of the two Fe(CO)3
groups, a doublet signal with an appreciably larger carbon-
˚
Figure 1. Molecular structure of 10a. Selected bond lengths [A]
phosphorus coupling constant of 27.1Ϫ28.8 Hz is found for and angles [°]: Fe(1)ϪC(3Ј) 2.037(3), Fe(1)ϪP(1) 2.2078(9),
each CO ligand of the second transition metal fragment.
Fe(1)ϪFe(2) 2.6493(6), Fe(2)ϪC(3Ј) 2.102(3), Fe(2)ϪC(2Ј)
2.135(3), Fe(2)ϪP(1Ј) 2.3684(12), P(1)ϪC(2) 1.773(3), P(1)ϪC(3)
The occurrence of different signals for the carbonyl ligands
of this Fe(CO)3 group confirms a hindered exchange be-
tween the axial and equatorial positions of the carbonyl
ligands. Since the η3-coordination of the 1-phosphaallyl
fragment creates high steric demands, these signals may
safely be assigned to the tricarbonyliron fragment of this
structural increment.
1.795(3), P(1)ϪP(1Ј) 2.1597(11), P(1Ј)ϪC(2Ј) 1.811(3), C(2)ϪC(3)
1.341(4), C(2Ј)ϪC(3Ј) 1.445(4); C(3Ј)ϪFe(1)ϪP(1) 83.08(10),
C(3Ј)ϪFe(2)ϪC(2Ј) 39.87(12), C(3Ј)ϪFe(2)ϪP(1Ј) 76.14(10),
C(2Ј)ϪFe(2)ϪP(1Ј)
47.07(8),
C(2)ϪP(1)ϪC(3)
44.16(14),
C(2)ϪP(1)ϪP(1Ј) 115.28(10), C(3)ϪP(1)ϪP(1Ј) 118.56(11),
C(2Ј)ϪP(1Ј)ϪP(1)
C(2)ϪC(3)ϪP(1)
92.56(10),
67.0(2),
C(3)ϪC(2)ϪP(1)
C(3Ј)ϪC(2Ј)ϪP(1Ј)
68.82(18),
115.8(2),
C(2Ј)ϪC(3Ј)ϪFe(1) 125.2(2)
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073
2069

J. Simon, G. J. Reiß, U. Bergsträßer, H. Heydt, M. Regitz
FULL PAPER
The resultant ORTEP plot clearly reveals the opening of gand and formation of an FeϪC σ-bond and the FeϪFe
one of the two phosphirene rings with formation of an η3 single bond.
complexed 1-phosphaallyl system. The crystal structure
analysis also confirms the formation of an iron-iron single
bond (see below), as well as the retention of the second
˚
phosphirene ring. The Fe1ϪP1 bond length of 2.208(9) A
is in the typical range for an iron complexed phosphane,[17]
and is comparable with the iron-phosphorus bond length in
9a. On the other hand, the FeϪP1Ј bond length in the 1-
˚
phosphaallyl unit of 2.368(1) A is appreciably stretched in
comparison with those of other η3-phosphaallyl-iron com-
plexes.[15] This is readily explained by the steric require-
ments of the substituents that force the Fe(CO)3 fragment
away from the 1-phosphaallyl unit. The iron-carbon separa-
tions in this structural increment are almost identical to
those in a comparable compound formed by the reaction
the µ3-RP bridged cluster (µ3-RP)Fe3(CO)10 with terminal
alkynes.[15] The bond lengths in the phosphaallyl unit of
˚
˚
1.811(3) A (P1ЈϪC2Ј) and 1.445(4) A (C2ЈϪC3Ј) are clearly
lengthened, and are of magnitudes typical for single bonds.
This is probably due to the enormous spatial requirements
of the substituents. The ironϪiron bond length of 2.6493(6)
˚
A in 10a is also of a typical magnitude for this type of
single bond.[15] The P1ϪP1Ј-bond length of 2.159(1) A is
˚
Scheme 6
considerably shortened in comparison with those of uncom-
plexed phosphanes or that of 9a.[18] This observation can
be rationalized by the ring-bracketing effect of the FeϪC-
3Ј bond. The intracyclic bonding parameters of the intact
phosphirene ring of 10a are in the typical ranges for a trans-
ition-metal complexed 1H-phosphirene.[12]
Experimental Section
General Remarks: The reactions were carried out under an atmo-
sphere of argon (purity Ͼ 99.998%) in a previously baked-out and
evacuated apparatus (Schlenk techniques). The solvents were dried
by standard procedures (n-pentane and diethyl ether: Na/K alloy),
distilled and stored under argon. Ϫ Melting points: Mettler FP 61
(heating rate: 3 °C/min). Ϫ FT-IR spectra: PerkinϪElmer infrared-
spectrometer 16PC. Ϫ Mass spectra: Finnigan MAT 90 spectro-
meter. Ϫ NMR spectra: Bruker AMX 400 (1H: 400 MHz, 13C:
101 MHz) and Bruker AC 200 (1H: 200 MHz, 13C: 50 MHz, 31P:
81 MHz) spectrometers, solvent as internal standard (1H and 13C);
the chemical shifts for 31P are relative to external 85% ortho-
phosphoric acid. Ϫ Compounds 5a and 5b were prepared by pub-
lished methods.[13] Disodium tetracarbonylferrate was purchased
from Aldrich and used without further purification.
On the basis of 31P{1H} NMR monitoring of the
photolysis reaction of 9a a multi-step sequence can be as-
sumed. By comparison of the resonance signals of the vari-
ous intermediates with those of known compounds, the fol-
lowing mechanism can be proposed:
The initial step in the formation of 10 could be the inser-
tion of one of the two Fe(CO)4 fragments into a PϪC bond
of the coordinatively attached three-membered ring sys-
tems. This results in the intermediate 11, in which a metalla-
phosphacyclobutene system is linked to a complexed phos-
phirene system (Scheme 6). The signal for the phosphorus
atom in the three-membered ring of 11a appears in the
31P{1H} NMR spectrum of the reaction solution as a doub-
let at δ ϭ Ϫ99.5 (1JP,P ϭ 322.4 Hz). A further doublet with
the same coupling constant is seen at δ ϭ 56.0. This chem-
ical shift value is typical for a compound with a metallapho-
sphacyclobutene skeleton as revealed by a comparison with
an analogous rhodium complex.[19] The subsequent cleav-
age of a carbonyl ligand from the Fe(CO)4 fragment of the
four-membered ring then initiates the conversion of the η2-
Column chromatography was formed in water-cooled glass tubes
with a positive pressure of argon on the column. Silica gel and
neutral aluminum oxide were heated for 5 h under vacuum and
then deactivated with 4% water.
Synthesis of the (1,1Ј-Bi-1H-phosphirene)iron Complexes 7a and 7b.
؊ General Procedure: To a suspension of disodium tetracarbonyl-
ferrate in diethyl ether (30 mL) was added dropwise with stirring
at Ϫ78 °C a solution of two equivalents of the corresponding 1-
chloro-1H-phosphirene 5 in diethyl ether (20 mL). The reaction
mixture was allowed to warm up to room temp. with stirring. The
coordinated complex 11 with ring opening to the 16-valence mixture was then evaporated under vacuum and the residue puri-
fied by column chromatography on silica gel with n-pentane/diethyl
ether [40:1 (7a), 100:1 (7b)] as eluent. The yellow eluate was evapor-
ated to dryness and the resulting red solid was recrystallized from
n-pentane at Ϫ28 °C to yield pure 7 as orange-yellow crystals.
electron carbene complex 12. The PϭC double bond of the
phosphaalkene system in 12a gives rise to a 31P{1H} NMR
signal at δ ϭ 282.1. This value is in the typical range for a
phosphaalkene. Since the 16-VE fragment in 12 is coordin-
atively unsaturated and thus possesses only a low stability,
[3,3Ј-Bis(1,1-dimethylethyl)-2,2Ј-diphenyl-1,1Ј-bi-1H-phosphirene-
subsequent rearrangement occurs with cleavage of a CO li- κP1]tetracarbonyliron (7a): Starting materials: 791 mg (3.52 mmol)
2070
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073

Synthesis and Reactions of (1,1Ј-Bi-1H-phosphirene)iron Complexes
1-chloro-3-(1,1-dimethylethyl)-2-phenyl-1H-phosphirene
FULL PAPER
(28) [C13H16ϩ], 157 (14) [C12H13ϩ], 143 (100) [C11H11ϩ], 128 (23)
609 mg (1.76 mmol) disodium tetracarbonylferrate. Ϫ Yield 560 mg [C10H8ϩ]. Ϫ HR-MS (EI, 70 eV); [Mϩ]: calcd. 574.1135; found
(58%), orange-yellow crystals, mixture of two diastereomers (ratio 574.1130.
(5a),
8:1). Ϫ m.p.: 97 Ϫ 99 °C. Ϫ IR (CCl4, cmϪ1): ν˜ ϭ 2966 (w), 2042
Synthesis of the (1,1Ј-Bi-1H-phosphirene)diiron Complexes 9a, b. ؊
General Procedure: A mixture of the diastereomers of the corres-
ponding mono complexed 1,1Ј-bi-1H-phosphirenes 7 was dissolved
in n-pentane and treated with an excess of nonacarbonyldiiron. The
suspension was stirred at room temp. for 24 h. The resulting dark
red reaction solvents were evaporated to dryness. The brown res-
idue was purified by column chromatography on neutral aluminum
oxide with n-pentane as eluent. Recrystallization from n-pentane
gave products 9a and 9b as yellow crystals.
(s, CO), 1971 (m, CO), 1939 (vs, CO), 1474 (w), 1072 (m), 1008
(m), 620 (s). Ϫ 31P{1H} NMR (CDCl3): major diastereomer: δ ϭ
1
1
Ϫ88.1 (d, JP,P ϭ 427.3 Hz, P-1), Ϫ134.2 (d, JP,P ϭ 427.3 Hz, P-
1
1Ј); minor diastereomer: δ ϭ Ϫ86.8 (d, JP,P ϭ 427.1 Hz, P-1),
Ϫ132.6 (d, JP,P ϭ 427.1 Hz, P-1Ј). Ϫ 1H NMR (CDCl3): major
1
diastereomer: δ ϭ 1.44 [s, broad, 18 H, C(CH3)3]; minor diastere-
omer: δ ϭ 1.50 [s, broad, 18 H, C(CH3)3]. Ϫ 13C{1H} NMR
(CDCl3): not all signals could be assigned because of overlapping
3
effects: major diastereomer: δ ϭ 29.2 [d, JC,P ϭ 1.7 Hz, C(CH3)3],
2
3
29.5 [s, C(CH3)3], 33.9 [dd, JC,P ϭ 6.4 Hz, JC,P ϭ 3.0 Hz,
[µ-[3,3Ј-Bis(1,1-dimethylethyl)-2,2Ј-diphenyl-1H-phosphirene-
κP1:κP1Ј]]octacarbonyldiiron (9a): Starting materials: 404 mg
(0.74 mmol) 7a, 538 mg (1.48 mmol) nonacarbonyldiiron. Ϫ Yield
330 mg (63%), yellow crystals, mixture of two diastereomers (ratio
2
1
C(CH3)3], 34.2 [d, JC,P ϭ 6.8 Hz, C(CH3)3], 120.3 (d, JC,P
50.8 Hz, C-2Ј), 124.8 (dd, JC,P ϭ 22.0 Hz, JC,P ϭ 4.2 Hz, C-2),
127.3 (d, JC,P ϭ 7.6 Hz, Ph), 128.6 (s, Ph), 128.9 (s, Ph), 129.7 (d,
ϭ
1
2
10:1). Ϫ m.p.: 135 °C (decomposition). Ϫ IR (KBr, cmϪ1): ν ϭ
J
C,P ϭ 5.1 Hz, Ph), 130.4 (d, JC,P ϭ 4.2 Hz, Ph), 131.3 (s, Ph), 138.5
˜
1
1
2
(d, JC,P ϭ 57.7 Hz, C-3Ј), 140.5 (dd, JC,P ϭ 27.1 Hz, JC,P
5.1 Hz, C-3), 213.9 (d, JC,P ϭ 19.5 Hz, CO); minor diastereomer:
ϭ
2968 (m), 2930 (w), 2060 (s, CO), 2044 (s, CO), 1948 (vs, CO), 1938
(vs), 1098 (w), 1026 (w), 798 (w), 622 (m), 610 (m). Ϫ 31P{1H}
NMR (CDCl3): major diastereomer: δ ϭ Ϫ69.3 (s); minor diastere-
omer: δ ϭ Ϫ66.8 (s). Ϫ 1H NMR (CDCl3): major diastereomer: δ ϭ
1.52 [s, 18 H, C(CH3)3]; minor diastereomer: δ ϭ 1.49 [s, 18 H,
C(CH3)3]. Ϫ 13C{1H} NMR (CDCl3): not all signals could be as-
signed because of overlapping effects: major diastereomer: δ ϭ 29.3
[pseudo-t, |3JC,P ϩ 4JC,P| ϭ 4.2 Hz, C(CH3)3], 34.8 [pseudo-t, |2JC,P
2
3
δ ϭ 29.2 [s, C(CH3)3], 29.4 [d, JC,P ϭ 2.5 Hz, C(CH3)3], 34.3 [d,
2JC,P ϭ 5.9 Hz, C(CH3)3], 121.3 (dd, JC,P ϭ 48.9 Hz, JC,P
ϭ
1
2
1
2
2.6 Hz, C-2Ј), 125.0 (dd, JC,P ϭ 33.7 Hz, JC,P ϭ 3.4 Hz, C-2),
127.2 (d, JC,P ϭ 11.0 Hz, Ph), 128.6 (s, Ph), 129.7 (d, JC,P ϭ 5.1 Hz,
1
Ph), 130.3 (d, JC,P ϭ 4.2 Hz, Ph), 131.2 (s, Ph), 135.6 (d, JC,P
ϭ
1
2
56.2 Hz, C-3Ј), 141.8 (dd, JC,P ϭ 26.3 Hz, JC,P ϭ 4.2 Hz, C-3),
214.2 (d, JC,P ϭ 18.7 Hz, CO). Ϫ MS (EI, 70 eV): m/z (%) ϭ 546
2
ϩ
3JC,P| ϭ 3.4 Hz, C(CH3)3], 126.1 (pseudo-t, |3JC,P
ϩ
4JC,P| ϭ
(8) [Mϩ], 434 (41) [Mϩ Ϫ 4CO], 276 (100) [Mϩ Ϫ 4CO Ϫ C12H14],
98 (43) [C2P2Fe(CO)2ϩ], 189 (68) [C12H14Pϩ], 143 (26) [C11H11ϩ].
Ϫ C28H28FeP2O4 (546.32 g/mol): calcd. C 61.56, H 5.17; found C
60.90, H 5.07. Ϫ HR-MS (EI, 70 eV); [Mϩ]: calcd. 546.0813;
found 546.0813.
2
3.4 Hz, o-Ph), 128.5 (pseudo-t, |1JC,P ϩ JC,P| ϭ 15.2 Hz, C-2ϪC-
2Ј), 128.9 (s, m-Ph), 130.4 (pseudo-t, |2JC,P
ϩ
3JC,P| ϭ 5.9 Hz, i-
Ph), 130.6 (d, JC,P ϭ 1.7 Hz, p-Ph), 142.2 (pseudo-t, |1JC,P
ϩ
5
2JC,P| ϭ 22.0 Hz, C-3ϪC-3Ј), 213.1 (pseudo-t, |2JC,P
ϩ
3JC,P| ϭ
17.0 Hz, CO); minor diastereomer: δ ϭ 29.7 [pseudo-t, |3JC,P
ϩ
4JC,P| ϭ 5.0 Hz, C(CH3)3], 34.7 [pseudo-t, |2JC,P ϩ JC,P| ϭ 3.4 Hz,
3
[3,3Ј-Bis(1,1-dimethylpropyl)-2,2Ј-diphenyl-1H-phosphirene-κP1]-
tetracarbonyliron (7b): Starting materials: 649 mg (2.72 mmol) 1-
C(CH3)3], 126.0 (pseudo-t, |3JC,P
ϩ
4JC,P| ϭ 3.4 Hz, o-Ph), 142.3
(pseudo-t, |1JC,P
ϩ
2JC,P| ϭ 20.4 Hz, C-3ϪC-3Ј), 213.2 (pseudo-t,
chloro-3-(1,1-dimethylpropyl)-2-phenyl-1H-phosphirene
(5b),
|2JC,P ϩ JC,P| ϭ 17.8 Hz, CO). Ϫ MS (EI, 70 eV): m/z (%) ϭ 714
(0.02) [Mϩ], 490 (72) [Mϩ Ϫ 8CO], 434 (14) [Mϩ Ϫ Fe Ϫ 8CO],
332 (100) [Mϩ Ϫ 8CO Ϫ C12H14], 287 (24) [Mϩ Ϫ 8CO Ϫ C12H14
Ϫ 3CH3], 276 (49) [Mϩ Ϫ Fe Ϫ 8CO Ϫ C12H14], 158 (36)
[C12H14؉], 143 (96) [C11H11؉]. Ϫ C32H28Fe2P2O8 (714.21 g/mol):
calcd. C 53.82, H 3.95; found C 53.12, H 4.20.
3
471 mg (1.36 mmol) disodium tetracarbonylferrate. Ϫ Yield 470 mg
(60%), orange-yellow solid, mixture of two diastereomers (ratio
4:1). Ϫ IR (KBr, cmϪ1): ν˜ ϭ 2967 (s), 2934 (w), 2039 (vs, CO),
1963 (s, CO), 1938 (vs, CO), 1636 (m), 1464 (m), 1074 (s), 620 (s). Ϫ
31P{1H} NMR (CDCl3): major diastereomer: δ ϭ Ϫ90.6 (d, 1JP,P ϭ
1
427.6 Hz, P-1), Ϫ132.2 (d, JP,P ϭ 427.6 Hz, P-1Ј); minor diastere-
1
1
omer: δ ϭ Ϫ88.3 (d, JP,P ϭ 426.6 Hz, P-1), Ϫ132.3 (d, JP,P
ϭ
µ-[3,3Ј-Bis(1,1-dimethylpropyl)-2,2Ј-diphenyl-1H-phosphirene-
426.6 Hz, P-1Ј). Ϫ 1H NMR (CDCl3): major diastereomer: δ ϭ 0.96 κP1:κP1Ј]octacarbonyldiiron (9b): Starting materials: 471 mg
(t, 3 H, JH,H ϭ 7.6 Hz, CH2ϪCH3), 1.12 (t, 3 H, JH,H ϭ 7.0 Hz, (0.82 mmol) 7b, 597 mg (1.64 mmol) nonacarbonyldiiron. Ϫ Yield
CH2ϪCH3), 1.42, 1.43, 1.46, 1.47 [each s, 12 H, C(CH3)2CH2], 1.63 330 mg (54%), mixture of two diastereomers (ratio 6:1). Ϫ IR (KBr,
3
3
Ϫ 1.92 (m, 4 H, CH2ϪCH3; minor diastereomer: the signals could
cmϪ1): nu(tide) ϭ 2970 (w), 2044 (s, CO), 1982 (m, CO), 1936 (vs,
not be assigned because of overlapping effects. Ϫ 13C{1H} NMR CO), 1468 (w), 1444 (w), 760 (m). Ϫ 31P{1H} NMR (CDCl3): major
(CDCl3): not all signals could be assigned because of overlapping
diastereomer: δ ϭ Ϫ70.5 (s); minor diastereomer: δ ϭ Ϫ67.4 (s). Ϫ
4
effects: major diastereomer: δ ϭ 8.7 (d, JC,P ϭ 6.3 Hz, CH2-CH3), 1H NMR (CDCl3): major diastereomer: δ ϭ 0.90 (t, 3JH,H ϭ 7.2 Hz,
4
9.1 (d, JC,P ϭ 4.5 Hz, CH2-CH3), 25.7 [s, C(CH3)2], 26.2 [d,
6 H, CH2ϪCH3), 1.42, 1.45 [each s, 12 H, C(CH3)2CH2], 1.80 (q,
3JC,P ϭ 5.4 Hz, C(CH3)2], 26.5 [s, C(CH3)2], 26.9 [s, C(CH3)2], 34.4 3JH,H ϭ 7.2 Hz, 4 H, CH2ϪCH3); minor diastereomer: the signals
3
(d, JC,P ϭ 5.4 Hz, CH2ϪCH3), 34.4 (s, CH2ϪCH3), 37.0 [s, could not be assigned because of overlapping effects and low in-
1
C(CH3)2Et], 37.7 [d, 2JC,P ϭ 5.4 Hz, C(CH3)2Et], 120.9 (d, JC,P ϭ
tensity signals. Ϫ 13C{1H} NMR (CDCl3): major diastereomer: δ ϭ
1
3
4
51.2 Hz, C-2Ј), 125.1 (d, JC,P ϭ 22.4 Hz, C-2), 127.0 (d, JC,P
ϭ
8.8 (d, JC,P ϭ 8.8 Hz, CH2-CH3), 26.0 [s, C(CH3)2Et], 26.2 [s,
3
3
2
8.3 Hz, o-Ph), 127.2 (d, JC,P ϭ 7.2 Hz, o-Ph), 128.3 (s, Ph), 128.6 C(CH3)2Et], 34.2 (d, JC,P ϭ 10.4 Hz, CH2ϪCH3), 38.3 [d, JC,P
ϭ
2
2
1
(s, Ph), 129.4 (d, JC,P ϭ 16.2 Hz, i-Ph), 129.5 (d, JC,P ϭ 14.4 Hz, 14.5 Hz, C(CH3)2Et], 126.3 (d, JC,P ϭ 20.0 Hz, C-2ϪC-2Ј), 128.9
i-Ph), 130.1 (s, Ph), 131.2 (s, Ph), 138.3 (d, JC,P ϭ 57.5 Hz, C-3Ј), (s, m-Ph), 129.9 (pseudo-t, |2JC,P ϩ 3JC,P| ϭ 7.2 Hz, i-Ph), 130.4 (d,
1
1
2
2
5
141.4 (dd, JC,P ϭ 28.3 Hz, JC,P ϭ 4.0 Hz, C-3), 213.7 (d, JC,P
ϭ
3JC,P ϭ 6.4 Hz, o-Ph), 130.5 (d, JC,P ϭ 3.2 Hz, p-Ph), 141.6
18.0 Hz, CO); minor diastereomer: δ ϭ 34.2 (s, CH2ϪCH3), 35.8 [s, (pseudo-t, |1JC,P ϩ JC,P| ϭ 12.0 Hz, C-3ϪC-3Ј), 213.7 (d, JC,P
ϭ
2
2
C(CH3)2Et], 125.0 (d, 1JC,P ϭ 21.5 Hz, C-2), 128.3 (s, Ph), 128.6 (s, 4.8 Hz, CO); minor diastereomer: the signals could not be assigned
1
Ph), 130.0 (s, Ph), 130.9 (s, Ph), 134.8 (d, JC,P ϭ 59.2 Hz, C-3Ј),
because of overlapping effects and low intensity signals. Ϫ MS (EI,
139.9 (d, JC,P ϭ 27.8 Hz, C-3), 214.1 (d, JC,P ϭ 18.0 Hz, CO). Ϫ 70 eV): m/z (%) ϭ 742 (0.04) [Mϩ], 518 (24) [Mϩ Ϫ 8CO], 346 (38)
1
2
MS (EI, 70 eV): m/z (%) ϭ 574 (1) [Mϩ], 462 (7) [Mϩ Ϫ 4CO], 172
[Mϩ Ϫ 8CO Ϫ C13H16], 290 (29) [Mϩ Ϫ Fe Ϫ 8CO Ϫ C13H16],
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073
2071

J. Simon, G. J. Reiß, U. Bergsträßer, H. Heydt, M. Regitz
FULL PAPER
143 (100) [C11H11ϩ], 128 (20) [C10H8ϩ].
Ϫ
C34H32Fe2P2O8 ting, are more or less separated (twinning by reticular meohedry).
(742.26 g/mol): calcd. C 55.02, H 4.35; found C 53.95, H 4.10.
The twin matrix evaluated from the orientation matrices of both
twin components was calculated to (1 0 0, 0 Ϫ1 0, Ϫ0.4526 0 Ϫ1).
Data collection on an IPDS-diffractometer has been performed us-
ing a light yellow crystal with the dimensions 0.30 ϫ 0.25 ϫ 0.20
mm3.
Photolysis of the (1,1Ј-Bi-1H-phosphirene)diiron Complexes 9a and
9b. ؊ General Procedure: A solution of 9a or 9b in C6D6 (1 Ϫ 2
mL) was irradiated with a high-pressure mercury lamp (λ Յ
280 nm) and the reaction was monitored by 31P NMR spectroscopy
(7 Ϫ 9 h). After evaporation of the solvent under vacuum the res-
idue was purified by column chromatography on neutral aluminum
oxide with n-pentane/diethyl ether (1:1) as eluent. Recrystallization
from n-pentane/diethyl ether (1:1) gave 10a and 10b as red crystals.
The standard integration and data reduction methods[20] results in
data sets, that only contain non-overlapped reflections. Structure
solution by direct methods and completion of the structure model
by difference Fourier synthesis using only these non-overlapping
reflections succeeded in the space group P21/n. For a twin refine-
ment in SHELXL-97[21] by the method of Pratt, Coyle, and Ibers[22]
for the overlapped reflections the sum of F2c values of the individual
twin components, each multiplied by its fraction contribution, was
fitted to the F2o value and its fraction contribution. Hence, the dif-
fractometer output has to be reformatted according to the above-
mentioned twin law, and all reflections that neither overlap exactly
nor can be resolved properly have been discarded. A simultaneous
refinement of both twin components converged to a twin ratio of
0.3957/0.6043(5). All hydrogen atoms were included in the last
stages of refinement in geometrically calculated positions, and their
Uiso values were set to 1.2 and 1.5 times the Ueq value of the corres-
ponding aromatic and methyl carbon atoms, respectively. Refine-
ment of 410 parameters based on 9292 reflections converged to
Hexacarbonyl-µ-[η1:η3-{1-[2Ј-(1,1-Dimethylethyl)-3Ј-phenyl-1Ј-
phosphapropenyl-κP1Ј:κC2Ј:κC3Ј]-3-(1,1-dimethylethyl)-2-phenyl-
1H-phosphirene-κP1}]diiron(Fe؊Fe) (10a): Starting material:
471 mg (0.66 mmol) (9a). Ϫ Yield 20 mg (5%), red crystals. Ϫ
1
31P{1H} NMR (CDCl3): δ ϭ Ϫ1.6 (d, JP,P ϭ 312.2 Hz, P-1Ј),
1
1
Ϫ70.4 (d, JP,P ϭ 312.2 Hz, P-1). Ϫ H NMR (CDCl3): δ ϭ 1.16,
1.42 [each s, 18 H, C(CH3)3]. Ϫ 13C{1H} NMR (CDCl3): δ ϭ 29.7
[d, JC,P ϭ 2.6 Hz, C(CH3)3], 34.1 [d, JC,P ϭ 2.6 Hz, C(CH3)3],
34.5 [d, 2JC,P ϭ 5.1 Hz, C(CH3)3], 41.0 [dd, 2JC,P ϭ 16.1 Hz, 3JC,P ϭ
3
3
1
1.7 Hz, C(CH3)3], 124.6 (d, JC,P ϭ 16.9 Hz, C-2), 126.6 (s, Ph),
127.1 (d, JC,P ϭ 6.8 Hz, Ph), 127.6 (s, Ph), 129.1 (s, Ph), 130.0 (s,
Ph), 130.5 (s, Ph), 130.9 (d, JC,P ϭ 5.1 Hz, Ph), 134.2 (s, Ph), 134.5
1
2
(s, Ph), 150.6 (d, JC,P ϭ 41.5 Hz, C-3), 153.9 (d, JC,P ϭ 2.5 Hz,
1
2
wR2(F2) ϭ 0.0781, R1(F) ϭ 0.0353 [for 6237 reflections with F2o Ͼ
C-3Ј), 191.2 (dd, JC,P ϭ 11.0 Hz, JC,P ϭ 5.1 Hz, C-2Ј), 205.4 [d,
2JC,P ϭ 27.6 Hz, Fe(CO)3], 209.2 [d, JC,P ϭ 27.1 Hz, Fe(CO)3],
˚
2
3
2σ(F2o)], GoF ϭ 1.029, ∆ρmin/∆ρmax ϭ Ϫ0.198/0.231 e/A , (∆/
2
2
211.4 [d, JC,P ϭ 28.8 Hz, Fe(CO)3], 212.4 [d, JC,P ϭ 6.8 Hz,
Fe(CO)3]. Ϫ MS (EI, 70 eV): m/z (%) ϭ 658 (0.06) [Mϩ], 490 (20)
[Mϩ Ϫ 6CO], 332 (34) [Mϩ Ϫ 6CO Ϫ C12H14], 158 (80) [C12H14ϩ],
σ)max ϭ 0.045.
Crystallographic data (excluding structure factors) for the structure
included in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
no. CCDC-157268. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK [Fax: (internat.) ϩ44Ϫ1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
143 (100) [C11H11ϩ], 128 (31) [C10H8ϩ].
Ϫ C30H28Fe2P2O6
(658.187 g/mol): calcd. C 54.75, H 4.29; found C 54.49, H 4.31.
Hexacarbonyl-µ-[η1:η3-{1-[2Ј-(1,1-Dimethylpropyl)-3Ј-phenyl-1Ј-
phosphapropenyl-κP1Ј:κC2Ј:κC3Ј]-3-(1,1-dimethylpropyl)-2-phenyl-
1H-phosphirene-κP1}]diiron(Fe؊Fe) (10b): Starting material:
401 mg (0.54 mmol) 9b. Ϫ Yield 20 mg (6%), red crystals. Ϫ
31P{1H} NMR (CDCl3): δ ϭ 4.2 (d, 1JP,P ϭ 315.2 Hz, P-1Ј), Ϫ69.5
1
1
(d, JP,P ϭ 315.2 Hz, P-1). Ϫ H NMR (CDCl3): δ ϭ 0.80 Ϫ 1.02
(m, 6 H, CH2ϪCH3), 1.17 [s, 3 H, C(CH3)2CH2], 1.38 [s, 9 H,
C(CH3)2CH2], 1.74 (m, 4 H, CH2ϪCH3). Ϫ 13C{1H} NMR
(CDCl3): δ ϭ 9.7 (s, CH2-CH3), 10.1 (s, CH2-CH3), 27.2 [d, 3JC,P ϭ
Acknowledgments
We thank the Landesregierung of Rheinland-Pfalz for a graduate
grant (to J. S.) and the Fonds der Chemischen Industrie for gener-
ous financial support.
3
2.5 Hz, C(CH3)2Et], 27.3 [d, JC,P ϭ 2.5 Hz, C(CH3)2Et], 31.8 [s,
3
3
C(CH3)2Et], 34.8 (d, JC,P ϭ 1.7 Hz, CH2ϪCH3), 37.7 (d, JC,P
ϭ
[1]
2
C. Peters, S. Stutzmann, H. Disteldorf, S. Werner, U. Berg-
0.9 Hz, CH2ϪCH3), 38.3 [d, JC,P ϭ 4.2 Hz, C(CH3)2Et], 43.8 [d,
2JC,P ϭ 14.4 Hz, C(CH3)2Et], 124.6 (d, 1JC,P ϭ 18.7 Hz, C-2), 126.1
(s, Ph), 126.7 (s, Ph), 128.2 (s, Ph), 128.4 (s, Ph), 128.7 (s, Ph), 129.0
(s, Ph), 129.1 (s, Ph), 129.4 (s, Ph), 130.1 (d, JC,P ϭ 21.2 Hz, Ph),
130.7 (d, JC,P ϭ 4.2 Hz, Ph), 150.4 (d, 1JC,P ϭ 44.1 Hz, C-3), 153.8
sträßer, C. Krüger, P. Binger, M. Regitz, Synthesis 2000, 529.
M. Regitz, in: Multiple Bonds and Low Coordination in Phos-
[2]
phorus Chemistry, (Eds. M. Regitz, O. J. Scherer), Thieme,
Stuttgart, 1990, p. 77Ϫ83.
G. Märkl, in: Multiple Bonds and Low Coordination in Phos-
[3]
2
1
2
(d, JC,P ϭ 0.9 Hz, C-3Ј), 192.9 (dd, JC,P ϭ 17.0 Hz, JC,P
ϭ
phorus Chemistry, (Eds. M. Regitz, O. J. Scherer), Thieme,
Stuttgart, 1990, p. 220Ϫ249.
J. Fink, W. Rösch, U.-J. Vogelbacher, M. Regitz, Angew. Chem.
7.6 Hz, C-2Ј), 205.0 [d, 2JC,P ϭ 30.6 Hz, Fe(CO)3], 205.6 [d, 2JC,P ϭ
2
[4]
27.1 Hz, Fe(CO)3], 209.3 [d, JC,P ϭ 25.4 Hz, Fe(CO)3], 212.5 [d,
2JC,P ϭ 5.1 Hz, Fe(CO)3]. Ϫ MS (EI, 70 eV): m/z (%) ϭ 686 (0.4)
[Mϩ], 346 (18) [Mϩ Ϫ 6 CO Ϫ C13H16], 172 (25) [C13H16ϩ], 143
(100) [C11H11ϩ], 128 (23) [C10H8ϩ].
1986, 98, 265Ϫ266; Angew. Chem. Int. Ed. Engl. 1986, 25,
280Ϫ282.
[5]
K. Blatter, W. Rösch, U.-J. Vogelbacher, J. Fink, M. Regitz,
Angew. Chem. 1987, 99, 67Ϫ68; Angew. Chem. Int. Ed. Engl.
1987, 26, 85Ϫ86.
Crystallographic Data for 10a: Crystallization of 10a from different
solvents and inspection of the crystals by preliminary X-ray crystal-
lographic studies, showed that all investigated specimens were
twinned. The twinning element was in all cases a twofold axis along
[100]. According to the metrical peculiarity of the monoclinic lat-
[6] [6a]
D. Böhm, F. Knoch, S. Kummer, U. Schmidt, U. Zenneck,
Angew. Chem. 1995, 107, 251Ϫ254; Angew. Chem. Int. Ed.
Engl. 1995, 34, 198Ϫ201. Ϫ [6b] N. Avarvari, L. Ricard, F. Ma-
they, P. Le Floch, O. Löber, M. Regitz, Eur. J. Org. Chem. 1998,
[6c]
2039Ϫ2045. Ϫ
M. Hofmann, H. Heydt, M. Regitz, Syn-
˚
tice constants [a ϭ 14.045(1), b ϭ 11.127(1), c ϭ 20.109(2) A, β ϭ
thesis 2001, 463Ϫ467.
3
˚
[7]
[7a] G. Märkl, in: Multiple Bonds and Low Coordination in Phos-
phorus Chemistry, (Eds. M. Regitz, O. J. Scherer), Thieme,
Stuttgart, 1990, p. 252Ϫ253. Ϫ [7b] Y. Kobayashi, I. Kumadaki,
99.077(10)°, V ϭ 3103.3(5) A , Z ϭ 4] all reflections hkl with h ϭ
0, 9, 11, Ϫ9, Ϫ11 overlap nearly exactly, while the reflections of all
other layers, depending on the resolution of the diffractometer set-
2072
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073

Synthesis and Reactions of (1,1Ј-Bi-1H-phosphirene)iron Complexes
FULL PAPER
[15] [15a]
A. Ohsawa, H. Hamana, Tetrahedron Lett. 1976, 3715Ϫ3716.
[7c] Y. Kobayashi, H. Hamana, S. Fujino, A. Ohsawa, I. Kuma-
daki, J. Am. Chem. Soc. 1980, 102, 252Ϫ255.
K. Knoll, O. Orama, G. Huttner, Angew. Chem. 1984, 96,
989; Angew. Chem. Int. Ed. Engl. 1984, 23, 976. Ϫ[15b] K. Knoll,
G. Huttner, T. Fässler, L. Zsolnai, J. Organomet. Chem. 1987,
327, 255Ϫ267.
[8] [8a]
A. Mack, F. Tabellion, C. Peters, A. Nachbauer, U. Berg-
[16] [16a]
sträßer, F. Preuss, M. Regitz, Phosphorus, Sulfur and Silicon
1999, 144/146, 261Ϫ264. [8b] A. Mack, M. Regitz, in: Advances
in Strained and Interesting Organic Molecules (Ed.: B. Halton),
Suppl. 1, JAI Press Inc., Cambridge, Conn., 1999, p. 199Ϫ221.
C. E. Sumner, Jr., J. A. Collier, R. Petitt, Organometallics
T. E. Snead, C. A. Mirkin, K.-
L. Lu, H. L. Beckman, G. L. Geoffroy, Organometallics 1992,
[16b]
1982, 1, 1350Ϫ1360. Ϫ
11, 942Ϫ954.
[9]
[17] [17a]
Short communication: J. Simon, U. Bergsträßer, M. Regitz,
F. W. B. Einstein, R. D. G. Jones, J. Chem. Soc., Dalton
[17b]
Chem. Commun. 1998, 867Ϫ868.
Y. Kabe, K. Ohkubo, H. Ishikawa, W. Ando, J. Am. Chem.
Trans. 1972, 442Ϫ446. Ϫ
Chem. 1980, 19, 159Ϫ165. Ϫ
R. E. Riley, R. E. Davis, Inorg.
R. L. Keiter, A. L. Rheing-
old, J. J. Hamerski, C. K. Castle, Organometallics 1983, 2,
[10]
[17c]
Soc. 2000, 122, 3775Ϫ3776.
A. Marinetti, F. Mathey, J. Fischler, A. Mitschler, J. Chem.
[11]
1635Ϫ1639.
[18]
[19]
Soc., Chem. Commun. 1984, 45Ϫ46.
D. G. Gilheany, in: The Chemistry of Organophosphorus Com-
pounds, Vol. 1 (Eds. S. Patai, F. R. Hartley), Wiley, Chichester,
1990, p. 9Ϫ50.
F. A. Ajulu, D. Carmichael, P. B. Hitchcock, F. Mathey, M. F.
Meidine, J. F. Nixon, L. Ricard, M. L. Riley, J. Chem. Soc.,
Chem. Commun. 1992, 750Ϫ752.
[12] [12a]
H. Heydt, in: Science of Synthesis, Vol. 9 (Eds. G. Maas,
[12b]
M. Regitz), Thieme, Stuttgart, 2000, p. 85Ϫ124. Ϫ
F. Ma-
they, M. Regitz, in: Comprehensive Heterocyclic Chemistry II,
Vol. 1A (Eds. A. R. Katritzky, C. W. Rees), Pergamon, Oxford,
1996, p. 227Ϫ304. Ϫ [12c]F. Mathey, Chem. Rev. 1990, 90,
997Ϫ1025.
[20]
[21]
Stoe & Cie., IPDS-Software, Vers. 2.87, Stoe & Cie. GmbH,
Darmstadt, 1998.
[13] [13a]
O. Wagner, M. Ehle, M. Regitz, Angew. Chem. 1989, 101,
227Ϫ229; Angew. Chem. Int. Ed. Engl. 1989, 28, 225Ϫ226. Ϫ
G. M. Sheldrick, SHELXL-97, Program for the refinement of
crystal structure, Universität Göttingen, 1997.
[13b]
O. Wagner, M. Ehle, M. Birkel, J. Hoffmann, M. Regitz,
[13c]
[22] [22a]
Chem. Ber. 1991, 124, 1207Ϫ1213. Ϫ
H. Heydt, M. Ehle,
C. N. Pratt, B. A. Coyle, J. A. Ibers, J. Chem. Soc. (A)
[22b]
S. Haber, J. Hoffmann, O. Wagner, A. Göller, T. Clark, M.
Regitz, Chem. Ber./Recueil 1997, 130, 711Ϫ723.
A. Marinetti, F. Mathey, J. Am. Chem. Soc. 1985, 107,
4700Ϫ4706.
1971, 2146Ϫ2151.
A 1982, 38, 817Ϫ820.
G. B. Jameson, Acta Crystallogr., Sect.
[14]
Received December 18, 2000
[I00476]
Eur. J. Inorg. Chem. 2001, 2067Ϫ2073
2073