Organometallic complexes of benzannelated phospholyls: Synthesis and characterization of benzophospholyl and the first iso-benzophospholyl metal complexes

Article abstract of DOI:10.1021/om040022k

A large-scale synthesis of the benzophospholyl (BP) ligand, 4, has been developed and employed in the synthesis of a series of manganese and iron complexes. Reaction between Li-BP and FeCp(CO)₂X (X = Br, I) resulted in the formation of [(μ₂-BP)Fe₂Cp₂(CO) ₄]X, while reaction of bis(1,1′-benzophospholyl) with [FeCp(CO)₂]₂ gave a mixture of isomers of (μ₂-BP)₂Fe₂Cp₂(CO)₂. The phosphine adduct (BP-Ph)Mn₂(CO)₉ was obtained from BP-Ph and Mn₂(CO)₁₀ and converted to (η⁵- BP)Mn(CO)₃ upon reaction with organometallic or organic radicals. A synthesis for phenyl-iso-benzophosphole (iBP-Ph) has been explored. The compound is highly reactive and polymerizes instantaneously and irreversibly. Polymerization of the iBP precursor was avoided in the novel partially hydrogenated derivative iBPH₂-Ph. Manganese complexes of iBP, 5, were obtained by reaction of iBP-H₂-Ph with Mn₂(CO) ₂10, resulting in the formation of η⁵-iBP-H ₂)Mn(CO)₃. Reaction of (η⁵-iBP-H ₂)Mn(CO)₃ with DDQ gave (η⁵-iBP)Mn(CO) ₃, the first metal complex of iBP.

Full text of DOI:10.1021/om040022k

Organometallics 2004, 23, 3683-3693
3683
Or ga n om eta llic Com p lexes of Ben za n n ela ted
P h osp h olyls: Syn th esis a n d Ch a r a cter iza tion of
Ben zop h osp h olyl a n d th e F ir st iso-Ben zop h osp h olyl
Meta l Com p lexes†
Andreas Decken,* Frank Bottomley, Brianne E. Wilkins, and Erin D. Gill
Department of Chemistry, University of New Brunswick, P.O. Box 45222,
Fredericton, New Brunswick, E3B 6E2, Canada
Received February 25, 2004
A large-scale synthesis of the benzophospholyl (BP) ligand, 4, has been developed and
employed in the synthesis of a series of manganese and iron complexes. Reaction between
Li-BP and FeCp(CO)2X (X ) Br, I) resulted in the formation of [(µ2-BP)Fe2Cp2(CO)4]X, while
reaction of bis(1,1′-benzophospholyl) with [FeCp(CO)2]2 gave a mixture of isomers of (µ2-
BP)2Fe2Cp2(CO)2. The phosphine adduct (BP-Ph)Mn2(CO)9 was obtained from BP-Ph and
Mn2(CO)10 and converted to (η5-BP)Mn(CO)3 upon reaction with organometallic or organic
radicals. A synthesis for phenyl-iso-benzophosphole (iBP-Ph) has been explored. The
compound is highly reactive and polymerizes instantaneously and irreversibly. Polymeri-
zation of the iBP precursor was avoided in the novel partially hydrogenated derivative iBP-
H2-Ph. Manganese complexes of iBP, 5, were obtained by reaction of iBP-H2-Ph with
Mn2(CO)10, resulting in the formation of (η5-iBP-H2)Mn(CO)3. Reaction of (η5-iBP-H2)Mn-
(CO)3 with DDQ gave (η5-iBP)Mn(CO)3, the first metal complex of iBP.
In tr od u ction
virtually unexplored anion 4 and its elusive isomer 5.
With respect to the bonding in complexes of dibenzo-
phospholyl (DBP, 3), we recently reported on the
synthesis and characterization of a series of DBP
manganese and iron complexes. DBP served as a bridg-
ing ligand in the σ-complexes (µ2-DBP)(µ2-Br)Mn2(CO)8,
6, (µ2-DBP)2Mn2(CO)8, 7, (µ2-DBP)2Fe2Cp2(CO)2, 8, and
[(µ2-DBP)Fe2Cp2(CO)4][X] (X ) Br, I), 9, and π-complex-
es of DBP were not observed.18,19
Phosphorus-containing aromatic heterocycles have
attracted much interest for their use as ligands in
organometallic complexes1-5 in particular catalysts.6-10
Structural diversity of their transition metal complexes
has been facilitated by the ability of phospholyls to ligate
metals in σ-, π-, and mixed-bonding modes. While
phosphinine and phospholyl ligands 1 and 2 have been
studied extensively and their high degree of aromaticity
has been established experimentally and theoreti-
cally,11-17 very little is known about their benzannelated
analogues 3 and 4, and complexes of 5 are unknown.
Our research program is concerned with the ligating
abilities of ligands 3-5, particularly in complexes of the
† This article is dedicated to Professor Alan H. Cowley, distinguished
mentor and friend, on the occasion of his 70th birthday.
* To whom correspondence should be addressed. E-mail: adecken@
unb.ca.
The tendency to form σ-complexes was attributed to
the high degree of benzannelation of the phospholyl
(1) Mathey, F. Coord. Chem. Rev. 1994, 137, 1.
(2) Mathey, F. Chem. Rev. 1988, 88, 429.
(3) Mathey, F.; Le Floch, P. Coord. Chem. Rev. 1988, 179-180, 771.
(4) Mathey, F. New J . Chem. 1987, 11, 585.
(5) Bansal, R. K.; Heinicke, J . Chem. Rev. 2001, 101, 3549.
(6) Brown, S. J .; Gao, X.; Harrison, D. G.; Koch, L.; Spence, R. E. v.
H.; Yap, G. P. A. Organometallics 1998, 17, 5445.
(7) J aniak, C.; Lange, K. C. H.; Versteeg, U.; Lentz, D.; Budzelaar,
P. H. M. Chem. Ber. 1996, 129, 1517.
(8) J aniak, C.; Versteeg, U.; Lange, K. C. H.; Weimann; R.; Hahn,
I. J . Organomet. Chem. 1995, 501, 219.
(9) Mathey, F. J . Organomet. Chem. 2002, 646, 15.
(10) Weber, L. Angew. Chem., Int. Ed. 2002, 41, 563.
10.1021/om040022k CCC: $27.50 © 2004 American Chemical Society
Publication on Web 06/19/2004

3684 Organometallics, Vol. 23, No. 15, 2004
Decken et al.
Sch em e 1
Sch em e 2
Sch em e 3
ligand, leading to a decreased ability to bind in a η5-
fashion. Coordination of a metal to the central five-
membered ring in DBP would result in a very unfavor-
able loss of local aromaticity in the six-membered rings.
This effect is reduced for the phosphindolyl ligands 4
and 5 because of the lower degree of benzannelation and
is absent for the phospholyl ligand 2 because it is not
benzannelated. We here report the large-scale synthesis
of 4, its manganese and iron complexes, and the first
metal complex of 5.
washing of the solid product for 11 or simple recrystal-
lization for 13, allowing the facile and rapid synthesis
of 13 on a 9 g scale. Benzophosphole 13 was readily
converted into its anion, 4, by reaction with metallic
lithium, or to the bisphospholyl 14 by quenching 4 with
I2. Both 4 and 14 were most conveniently used in situ.
All organic products were characterized using standard
1H, 13C, and 31P NMR spectroscopies, mass spectrom-
etry, and in the case of 11 and 13, X-ray crystallography.
Com p lexes of Ben zop h osp h olyl 4. In light of the
facile synthesis and high stability of phosphacyman-
trenes27,28 and phosphaferrocenes,29-31 we prepared
manganese and iron complexes of 4. Reaction of 4 with
FeCp(CO)2X (X ) I, Br) lead to the isolation of 15 and
16 in high yields (49-74%) (Scheme 2).
Resu lts a n d Discu ssion
Syn th esis of Ben zop h osp h olyl 4. Several literature
procedures are available for the synthesis of 13, the
precursor to 4. However, they are lengthy or unreliable
or give poor overall yields.20-26 The most promising
route was that of Tsuchiya et al.,24,25 yielding 13 in four
steps from commercially available starting materials in
reasonable yields. Drawbacks of their strategy include
lengthy workup procedures and the formation of varying
quantities of the byproduct 12. Our approach involved
the preparation of 11 from 10 by reaction with BuLi,
ring closure with PhPCl2, and aerial oxidation. The
synthetic sequence was completed by removal of the tms
group with TBAF and reduction to 13 using HSiCl3
(Scheme 1).
Reaction between 14 and Fe2Cp2(CO)4 yielded the
metallacycle 17 (Scheme 3). Complex 17 consisted of a
The overall yield was 20%, but more importantly,
purification steps were unnecessary for 12 or involved
(11) Clark, T.; Elvers, A.; Heinemann, F. W.; Hennemann, M.; Zeller,
M.; Zenneck, U. Angew. Chem., Int. Ed. 2000, 39, 2087.
(12) Dransfeld, A.; Nyulaszi, L.; Schleyer, P. v. R. Inorg. Chem. 1998,
37, 4413.
(13) Goldfuss, B.; Schleyer, P. v. R. Organometallics 1997, 16, 1543.
(14) Goldfuss, B.; Schleyer, P. v. R.; Hampel, F. Organometallics
1996, 15, 1755.
(15) Mathey, F. J . Organomet. Chem. 1994, 475, 25.
(16) Keglevich, G.; Bo¨cskei, Z.; Kesertii, G. M.; Ujsza´szy, K.; Quin,
L. D. J . Am. Chem. Soc. 1997, 119, 5095.
(17) Nyula´szi, L. Chem. Rev. 2001, 101, 1229.
(18) Decken, A.; Neil, M.; Bottomley, F. Can. J . Chem. 2001, 79,
1321.
(19) Decken, A.; Neil, M.; Bottomley, F. Can. J . Chem. 2002, 80,
55.
(20) Chan, T. H.; Wong, L. T. L. Can. J . Chem. 1971, 49, 530.
(21) Quin, L. D.; Rao, N. S.; Topping, R. J .; McPhail, A. T. J . Am.
Chem. Soc. 1986, 108, 4519.
mixture of four isomers, 17a -d , inseparable by column
chromatography or crystallization.
(22) Quin, L. D.; Rao, N. S. J . Am. Chem. Soc. 1983, 105, 5960.
(23) Ashe, A. J .; Savla, P. M. J . Organomet. Chem. 1993, 461, 1.
(24) Kurita, J .; Ishii, M.; Yasuike, S.; Tsuchiya, T. Chem. Pharm.
Bull. 1994, 42, 1437.
(25) Kurita, J .; Ishii, M.; Yasuike, S.; Tsuchiya, T. J . Chem. Soc.
1993, 17, 1309.
(27) Mathey, F. Tetrahedron Lett. 1976, 4155.
(28) Mathey, F.; Mitschler, A.; Weiss, R. J . Am. Chem. Soc. 1978,
100, 5748.
(29) Mathey, F.; Mitschler, A.; Weiss, R. J . Am. Chem. Soc. 1977,
99, 3537.
(30) Mathey, F. J . Organomet. Chem. 1977, 139, 77.
(31) De Lauzon, G.; Deschamps, B.; Fischer, J.; Mathey, F.; Mitschler,
A. J . Am. Chem. Soc. 1980, 102, 994.
(26) Nief, F.; Charrier, C.; Mathey, F.; and Simalty, M. Phosphorus
Sulfur 1982, 13, 259.

Organometallic Benzannelated Phospholyl Complexes
Organometallics, Vol. 23, No. 15, 2004 3685
Sch em e 4
Sch em e 5
In both types of complexes, the BP ligand bridges two
metal atoms through the phosphorus atom, and bonding
involving the ligand π-electron system was not observed.
This behavior parallels that of the DBP ligand in the
complexes 8 and 9, as well as the manganese compounds
(µ2-BP)(µ2-Br)Mn2(CO)8 and (µ2-BP)2Mn2(CO)8.26 Com-
plexes 15-17 were characterized by 1H, 13C, and 31P
NMR and IR spectroscopies, mass spectrometry, and
microanalysis (15) and X-ray crystallography (16).
Complexes 15, 16, and 17 were mildly air and moisture
sensitive; 15 and 16 decomposed slowly, especially in
the presence of light, while 17 was indefinitely stable
under an inert atmosphere. Heating complexes 15, 16,
and 17 for extended periods yielded intractable decom-
position products.
To date, there are no crystallographically authenti-
cated η5-complexes of 4.32 The only account of a π-bond-
ed BP ligand is that of (η5-BP)Mn(CO)3, 19.26 The
generation of the benzophosphacymantrene 19 from
phosphole 13 and Mn2(CO)10 was in contrast to our
earlier observation that reaction between DBP-Ph and
Mn2(CO)10 led to the isolation of the phosphine adducts
20 and 21.18
diphosphine adduct 22 was not observed, in contrast to
the formation of the analogous DBP complex 21.
Heating 18 in refluxing xylenes resulted in decom-
position, yielding 13 as the only product containing
phosphorus. Liberation of the phosphine ligand was also
observed upon heating of the corresponding DBP com-
plexes 20 and 21. There was no evidence of a thermal
conversion of 18 to 19. However, reaction of 18 with
organic or organometallic radicals in xylenes led to the
formation of 19, indicated by a color change of the
solutions from orange-red to dark red and confirmed by
spectroscopic methods. Compound 19 can also be pre-
pared directly from 13 and Mn2(CO)10 upon extended
heating in refluxing xylenes, giving 19 in 17% yield. One
may conclude from these findings that 19 is produced
by attack of a radical on the hitherto unknown complex
18, contrary to the previously assumed pathway that
involved attack of a radical on 13.26 18 and 19 were
characterized by NMR and IR spectroscopies, mass
spectrometry, X-ray crystallography, and in the case of
18, microanalysis.
We consequently repeated the original literature
procedure and found that heating a mixture of 13 and
Mn2(CO)10 for 12 min resulted in the formation of 18
instead of 19 (Scheme 4). The orange-red oil was isolated
in 51% yield after flash chromatography and the
Attem p ted P r ep a r a tion of iso-Ben zop h osp h olyl
5. There are no literature reports on the synthesis of
the iso-benzophospholyl ligand 5 or its precursor 29. We
devised a strategy for their preparation starting from
23 (Scheme 5).
On the basis of literature precedence,33 23 was
converted to 24 by reaction with PhPCl2 in 81% yield.
(32) For substituted benzophospholyl complexes see: (a) Niecke, E.;
Nieger, M.; Wenderoth, P. Angew. Chem., Int. Ed. Engl. 1994, 33, 353.
(b) Nief, F.; Ricard, L. J . Organomet. Chem. 1994, 464, 149.
(33) Middlemas, E. D.; Quin, L. D. J . Org. Chem. 1979, 44, 2587.

3686 Organometallics, Vol. 23, No. 15, 2004
Decken et al.
Sch em e 6
heterocycle. Metal complexation was achieved upon
reaction of 31 with Mn2(CO)10, generating 32 as an
orange oil in 16% yield after flash chromatography. The
above reaction also produced 34 in trace amounts, but
the bis adduct 35 was not observed.
Hydrolysis gave the phosphine oxide 25 in 48% yield.
Aromatization of the six-membered ring was achieved
by reaction of 25 with DDQ to give known compound
26.33 Reduction with HSiCl3 gave phosphine 27 in 92%
yield, and bromination to give 28 was accomplished with
either Br2 or NBS, the former simplifying the workup
procedure and furnishing 28 in 78% yield. All products
were characterized by spectroscopic means and, in the
cases of 25 and 26, X-ray crystallography. Compound
27 was a highly air-sensitive colorless oil and 28 an air-
sensitive orange solid. Completion of the synthesis of
29 involved dehydrobromination of 28. Consequently,
28 was reacted with an excess of Et3N, resulting in the
immediate discoloration of the orange solution of 28 in
CH2Cl2, followed by the formation of a pale brown solid
precipitate and a pale brown solution. The solid was
insoluble in organic solvents. The solution showed no
signal in the in situ 31P NMR spectrum, and removal of
the solvent and excess Et3N yielded HEt3NBr as the
This behavior was identical to that of BP, 4, and in
contrast to that of DBP, 3. The final step in the
synthesis of a cymantrene analogue of iBP, 5, was the
dehydrogenation of 32 to give 33 as a yellow solid in
32% yield after sublimation. The novel complexes 32
1
and 33 have been fully characterized by H, 13C, and
31P NMR spectroscopies, mass spectrometry, high-
resolution mass spectrometry, and in the case of 33, IR
spectroscopy and X-ray crystallography. Complexes 32
and 33 are air and moisture sensitive, but are indefi-
nitely stable under an inert atmosphere. The isolation
of 33 is particularly important because it is the first
metal complex of the hitherto unknown ligand 5.34 The
synthesis of 19 and 33 proves that 4 and 5 form
π-complexes with manganese, in contrast to the behav-
ior of 3, for which only σ-complexes were obtained. This
substantiates the notion that the high degree of benz-
annelation in DBP, 3, eliminates the possibility of
forming η5-complexes, whereas the monobenzannelated
ligands 4 and 5 form stable cymantrene analogues.
1
only product, identified by H NMR and microanalysis.
On the basis of the dramatic color change upon addition
of base to 28 and the formation of HEt3NBr, one must
conclude that the dehydrobromination of 28 was suc-
cessful. These findings suggest that 29 was indeed
produced, but immediately polymerized, perhaps to give
30. It is easily envisaged that the driving force in such
a polymerization would be the gain of local aromaticity
in the six-membered ring of the iso-phosphindole skel-
eton. The polymerization was irreversible, and the
insoluble nature of the polymer prevented further
characterization.
Com p lexes of 5. The highly reactive nature of 29
prevented its use as a starting material in the synthesis
of organometallic complexes of 5, and we turned our
attention to precursors of 29 with a partially hydroge-
nated six-membered ring, eliminating the possibility of
polymerization (Scheme 6).
To this end, 24 was dehydrochlorinated with Et3N to
give 31 in 45% yield as a colorless, air-sensitive oil.
Dihydro-iso-phosphindole 31 was characterized by NMR
and IR spectroscopies, mass spectrometry, and high-
resolution mass spectrometry. The compound was stable
under an inert atmosphere, and formation of a polymer
analogous to 30 was not observed, confirming that
eliminating the possibility of aromatization of the six-
membered ring would increase the stability of the
Molecu la r Str u ctu r es
A thermal ellipsoid plot of 11 is shown in Figure 1,
and selected bond distances and angles are presented
in Table 3. The phosphindole skeleton is planar and the
phosphorus atom tetrahedrally coordinated. The P-C(8)
and P-O bond lengths fall within the expected ranges.
The five-membered ring contains an isolated CdC
double bond, indicated by the short C(2)-C(3) distance
of 1.3483(15) Å, and delocalization is not present. The
bond lengths within the five-membered heterocycle are
comparable to those of 13 (see below), and deformation
due to the bulky TMS group is not evident.
(34) For complexes of substituted neutral and cationic iso-benzo-
phospholyl ligands see: (a) Gudat, D.; Lewall, B.; Nieger, M.; Detmer,
I.; Szarvas, L.; Saarenketo; P.; Marconi, G. Chem. Eur. J . 2003, 9, 661.
(b) Gudat, D.; Holderberg, A. W.; Korber, N.; Nieger, M.; Schrott, M.
Z. Naturforsch., B: Chem. Sci. 1999, 54, 1244. (c) Gudat, D.; Hap, S.;
Szarvas, L.; Nieger, M. Chem. Commun. 2000, 1637. (d) Gudat, M.;
Nieger, M.; Schmitz, K.; Szarvas, L. Chem. Commun. 2002, 1820. (e)
Gudat, M.; Schrott, M.; Bajorat, V.; Nieger, M.; Kotila, S.; Fleischer,
R.; Stalke, D. Chem. Ber. 1996, 129, 337. (f) Gudat, M.; Hap, S.; Nieger,
M. J . Organomet. Chem. 2002, 643, 181. (g) Hap, S.; Nieger, M.; Gudat,
D.; Betke-Hornfeck, M.; Schramm, D. Organometallics 2001, 20, 2679.
(h) Bajko, Z.; Daniels, J .; Gudat, D.; Hap, S.; Nieger, M. Organome-
tallics 2002, 21, 5182. (i) Gudat, D.; Nieger, M.; Schrott, M. Chem.
Ber. 1995, 128, 259. (j) Gudat, M. Schrott, M.; Nieger, M. Chem.
Commun. 1995, 1541.

Organometallic Benzannelated Phospholyl Complexes
Organometallics, Vol. 23, No. 15, 2004 3687
Ta ble 1. Cr ysta l Da ta a n d Str u ctu r e Refin em en t for 11, 13, 16, a n d 18
11
13
16
18
formula
fw
C
17H19OPSi
C14H11
210.20
P
C22H16Fe2IO4P
613.92
C23H11Mn2O9P
572.17
298.38
cryst size, mm
color and habit
temperature, K
wavelength, Å
cryst syst
space group
a, Å
b, Å
0.075 × 0.150 × 0.375
colorless irregular
173(1)
0.71073
monoclininc
P21/n
6.8785(3)
22.5058(9)
10.9140(4)
90
106.811(1)
90
1617.35(11)
4
0.237
0.10 × 0.28 × 0.28
colorless irregular
173(1)
0.71073
orthorhombic
P2(1)2(1)2(1)
6.2210(8)
8.1465(11)
21.881(3)
90
0.175 × 0.275 × 0.35
Orange, irregular
173(1)
0.71073
orthorhombic
Pnma
12.9436(10)
12.5339(10)
13.3180(10)
90
90
90
0.175 × 0.45 × 0.525
yellow, irregular
173(1)
0.71073
monoclinic
C2/c
27.659(2)
13.1728(9)
13.1654(9)
90
100.556(3)
90
4715.6(6)
8
1.190
c, Å
R, deg
â, deg
90
90
γ, deg
V, Å3
1108.9(3)
4
0.208
2160.6(3)
4
2.872
Z
µ, mm-1
θ range, deg
no. of data measd
no. of unique data/R(int)
no. of restr/params
Sa (GOF) on F2
R1b (I>2σ(I))
wR2c (all data)
1.81 to 32.50
17 783
5781/0.0197
0/257
0.964
0.0367
1.86 to 32.48
9387
3832/0.0642
0/181
1.056
0.0624
2.19 to 32.50
22 627
4048/0.0333
0/189
1.085
0.0302
1.50 to 32.50
25 934
8487/0.0233
0/316
1.134
0.0519
0.0996
0.519, -0.183
0.1657
0.731, -0.336
0.0791
2.107, -0.683
0.1750
1.802, -0.655
∆
σmax, ∆σmin, e Å-3
S ) (∑[w(Fo - Fc2)2/(n - p))1/2
.
R1 ) ∑||(Fo| - |Fc||/∑|Fo|. c wR2 ) (∑[w(Fo - Fc2)2/∑[wFo4])1/2, where w-1 ) σ2(Fo2) + (aP)2 + bP,
a
2
b
2
where P ) (max (Fo2, 0) + 2Fc2)/3. For 11, a ) 0.0619, b ) 0; for 13, a ) 0.0962, b ) 0; for 16, a ) 0.0392, b ) 1.2121; for 18, a ) 0.0986,
b ) 0.
F igu r e 1. View of 11 showing the atom-numbering
scheme. Thermal ellipsoids are at the 30% probability level.
F igu r e 2. View of 13 showing the atom-numbering
scheme. Thermal ellipsoids are at the 30% probability level.
A thermal ellipsoid plot of 13 is presented in Figure
2, and selected bond distances and angles are sum-
marized in Table 4. The planar phosphindole skeleton
contains a localized CdC double bond between C(2) and
C(3) (1.326(4) Å) similar to that in 11. The P-C(8) bond
measures 1.852(2) Å, slightly elongated in comparison
to the phosphine oxide derivative 11 (1.8045(11) Å).
A thermal ellipsoid plot of the cation of 16 is depicted
in Figure 3, and selected bond distances and angles are
presented in Table 5. The phosphindolyl fragment lies
on a mirror plane, placing the phosphorus atom in a
tetrahedral environment. The Fe-P-Fe measures
125.04(3)° and is identical to those observed in 9a and
9b. However, the P-Fe (2.2690(4) Å) and Fe-Cp (Cp
) centroid of the cyclopentadienyl ring) (1.717 Å)
distances are slightly shorter than the corresponding
distances in 9a (P-Fe ) av 2.29 Å, Fe-Cp ) 1.73 Å)
and 9b (P-Fe ) av 2.30 Å, Fe-Cp ) 1.73 Å), most likely
due to the reduced steric demand of the benzophospholyl
ligand compared to the dibenzophospholyl ligand. The
Fe‚‚‚Fe distance is 4.026 Å, and therefore no direct
Fe-Fe interactions are observed. The iodide anion forms
five hydrogen bonds at 3.035 Å (H(2)), 3.084 Å (H(11)
and H(11a)), and 3.187 Å (H(8) and H(8′)). There are
no additional interionic contacts.
A thermal ellipsoid plot of 18 is shown in Figure 4,
and selected bond distances and angles are presented
in Table 6. The phosphine ligand is in an axial position
as expected for a bulky ligand, and the P-Mn-Mn
moiety is almost linear (177.69(2)°). The P-Mn
(2.2326(7) Å) and Mn-Mn distances (2.8870(5) Å)
compare favorably with those in 20 (P-Mn
)
2.2480(13) Å, Mn-Mn ) 2.9198(10) Å) and 21 (P-Mn
) 2.2223(7) and 2.2309(7) Å, Mn-Mn ) 2.8937(5) Å).
A thermal ellipsoid plot of 19 is shown in Figure 5,
and selected bond distances and angles are presented
in Table 7. The crystal lattice contains two independent
molecules per asymmetric unit, and their metric pa-
rameters are almost identical. The ligand skeleton is

3688 Organometallics, Vol. 23, No. 15, 2004
Ta ble 2. Cr ysta l Da ta a n d Str u ctu r e Refin em en t for 19, 25, 26, a n d 33
Decken et al.
19
25
26
33
formula
fw
C
11H6MnO3P
C14H15OP
230.23
C14H13OP
228.21
C11H6MnO3P
272.07
272.07
cryst size, mm
color and habit
temperature, K
wavelength, Å
cryst syst
space group
a, Å
b, Å
0.3 × 0.15 × 0.15
yellow, irregular
198(1)
0.71073
triclinic
0.075 × 0.4 × 0.4
colorless, irregular
198(1)
0.71073
monoclinic
P21/n
9.7371(10)
8.3018(9)
14.4596(15)
90
99.411(2)
90
1153.1(2)
4
0.213
2.35 to 24.96
5601
1944/0.0212
0/205
0.1 × 0.4 × 0.45
colorless, plate
198(1)
0.71073
triclinic
0.2 × 0.225 × 0.4
yellow, parallelepiped
198(1)
0.71073
triclinic
P1h
P1h
P1h
9.0111(7)
9.9967(8)
13.0257(10)
68.697(1)
81.642(1)
89.513(2)
1080.34(15)
4
10.0213(8)
10.8751(9)
11.3060(9)
87.160(2)
74.814(2)
88.958(2)
1187.65(17)
4
9.0278(4)
9.9626(5)
13.1254(6)
68.895(1)
81.148(1)
89.337(1)
1086.97(9)
4
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
µ, mm-1
1.354
1.70 to 27.50
7558
4726/0.0204
0/289
1.036
0.0393
0.1191
0.895, -0.663
0.206 mm
1.87 to 27.50
8327
5220/0.0131
0/393
1.068
0.0348
0.0983
0.443, -0.130
1.346
1.68 to 27.49
7615
4749/0.0170
0/337
1.060
0.0243
0.0698
0.322, -0.219
θ range, deg
no. of data measd
no. of unique data/R(int)
no. of restr/params
Sa (GOF) on F2
R1b (I>2σ(I))
wR2c (all data)
1.090
0.0362
0.1009
0.408, -0.198
∆
σmax, ∆σmin, e Å-3
S ) (∑[w(Fo - Fc2)2/(n - p))1/2
.
R1 ) ∑||(Fo| - |Fc||/∑|Fo|. c wR2 ) (∑[w(Fo - Fc2)2/∑[wFo4])1/2, where w-1 ) σ2(Fo2) + (aP)2 + bP,
a
2
b
2
where P ) (max (Fo2, 0) + 2Fc2)/3. For 19, a ) 0.0745, b ) 0.6516; for 25, a ) 0.0617, b ) 0.276; for 26, a ) 0.0609, b ) 0.2234; for 33,
a ) 0.0386, b ) 0.2151.
Ta ble 3. Selected Dista n ces (Å) a n d An gles (d eg)
for 11
P-O
1.4859(8)
O-P-C(1A)
116.05(5)
118.30(5)
93.76(5)
108.07(8)
126.79(8)
124.93(6)
116.9(1)
P-C(1A)
P-C(8)
1.8032(11)
1.8045(11)
1.8056(11)
1.3483(15)
1.8725(11)
1.4821(14)
1.3984(15)
O-P-C(2)
C(1A)-P-C(2)
C(3)-C(2)-P
C(3)-C(2)-Si
P-C(2)-Si
C(2)-C(3)-C(3A)
C(1A)-C(3A)-C(3)
C(3A)-C(1A)-P
P-C(2)
C(2)-C(3)
C(2)-Si
C(3)-C(3A)
C(3A)-C(1A)
112.73(9)
108.49(7)
Ta ble 4. Selected Dista n ces (Å) a n d An gles (d eg)
for 13
P-C(2)
1.815(3)
1.821(2)
1.842(2)
1.326(4)
1.471(4)
1.403(3)
C(2)-P-C(1A)
C(2)-P-C(8)
89.40(12)
102.78(12)
104.16(10)
113.0(2)
113.9(2)
113.0(2)
P-C(1A)
P-C(8)
C(1A)-P-C(8)
C(3)-C(2)-P
C(2)-C(3)
C(3)-C(3A)
C(3A)-C(1A)
C(2)-C(3)-C(3A)
C(1A)-C(3A)-C(3)
C(3A)-C(1A)-P
F igu r e 3. View of the cation of 16 showing the atom-
numbering scheme. Thermal ellipsoids are at the 30%
probability level.
110.15(16)
planar and bond delocalization in the five-membered
ring evident by the small deviation in inter atom
distances, ranging from 1.405(4) Å (C(2)-C(3)) to
1.430(4) Å (C(3a)-C(1a)) for C-C bonds and 1.777(3)
Å (P(1)-C(2)) to 1.796(3) Å (P(1)-C(1a)) for the P-C
bonds.35 The metal atom is coordinated to all five atoms
in the heterocycle, but slightly displaced away from
C(1a) and C(3a), resulting in a slipped η5-complex with
bond lengths ranging from 2.148(3) Å (Mn(1)-C(3)) and
2.153(3) Å (Mn(1)-C(2)) to 2.236(3) Å (Mn(1)-C(3A))
and 2.257(2) Å (Mn(1)-C(1A)). The Mn(1)-P(1) bond
measures 2.3833(8) Å, and the distance between the
centroid of the five-membered ring and the metal atom
is 1.799 and 1.803 Å for the two independent molecules,
Ta ble 5. Selected Dista n ces (Å) a n d An gles (d eg)
for 16
Fe-P
2.2690(4)
1.798(2)
1.813(2)
1.338(3)
1.450(3)
1.400(3)
C(2)-P-Fe
109.15(3)
108.66(3)
125.04(3)
111.64(18)
114.6(2)
P-C(2)
C(1A)-P-Fe
P-C(1A)
C(2)-C(3)
C(3)-C(3A)
C(3A)-C(1A)
Fe#1-P-Fe
C(3)-C(2)-P
C(2)-C(3)-C(3A)
C(1A)-C(3A)-C(3)
C(3A)-C(1A)-P
113.7(2)
109.21(16)
respectively. There is no significant deviation in the
Mn-CO bond lengths (av 1.796 Å), and the orientation
of the Mn(CO)3 tripod is analogous to that in substituted
(η5-indenyl)Mn(CO)3 complexes36-40 and (η5-2-methylin-
(36) Honan, N. B.; Atwood, J . L.; Bernal, I.; Hermann, W. A. J .
Organomet. Chem. 1979, 179, 403.
(37) Tamm, M.; Bannenberg, T.; Baum, K.; Frohlich, R.; Steiner.
T.; Meyer-Friedrichsen, T.; Heck, J . Eur. J . Inorg. Chem. 2000, 1161.
(38) Qian, C.; Guo, J .; Sun, J .; Chen, J .; Zheng, P. Inorg. Chem. 1997,
36, 1286.
(35) A very small disorder in one of the independent molecules,
interconverting the atom sites for P(2) and C(13), could not be modeled
properly. The disorder is evident by the observation of three peaks in
the Fourier difference map near C(13) and two peaks near P(2) and
results in the elongation of all bonds involving C(13). Bond lengths
for the disordered molecule have not been included in the discussion.
(39) Plenio, H.; Burth, D. Z. Anorg. Allg. Chem. 1996, 622, 225.

Organometallic Benzannelated Phospholyl Complexes
Organometallics, Vol. 23, No. 15, 2004 3689
F igu r e 4. View of 18 showing the atom-numbering
scheme. Thermal ellipsoids are at the 30% probability level.
F igu r e 6. View of 25 showing the atom-numbering
scheme. Thermal ellipsoids are at the 30% probability level.
F igu r e 7. View of one of the independent molecules of 26
showing the atom-numbering scheme. Thermal ellipsoids
are at the 30% probability level.
Ta ble 7. Selected Dista n ces (Å) a n d An gles (d eg)
for On e of th e In d ep en d en t Molecu les of 19
Mn(1)-C(3)
Mn(1)-C(2)
Mn(1)-C(3A)
Mn(1)-C(1A)
Mn(1)-P(1)
Mn(1)-C(10)
Mn(1)-C(9)
Mn(1)-C(8)
P(1)-C(2)
2.148(3)
2.153(3)
2.236(3)
2.257(2)
2.3833(8)
1.785(3)
1.799(3)
1.805(3)
1.777(3)
1.796(3)
1.405(4)
1.424(4)
1.430(4)
C(2)-P(1)-C(1A)
C(3)-C(2)-P(1)
C(2)-C(3)-C(3A)
C(3)-C(3A)-C(1A)
C(3A)-C(1A)-P(1)
88.68(14)
114.3(2)
112.2(3)
112.2(2)
112.6(2)
F igu r e 5. View of one of the independent molecules of 19
showing the atom-numbering scheme. Thermal ellipsoids
are at the 30% probability level.
Ta ble 6. Selected Dista n ces (Å) a n d An gles (d eg)
for 18
P-C(2)
1.790(3)
1.805(3)
1.811(2)
1.415(8)
1.517(9)
1.378(6)
2.2326(7)
2.8870(5)
C(2)-P-C(1A)
C(2)-P-C(8)
94.82(19)
101.48(16)
103.01(12)
116.46(10)
117.58(10)
119.54(8)
177.69(2)
104.7(4)
P-C(1A)
P(1)-C(1A)
C(2)-C(3)
P-C(8)
C(1A)-P-C(8)
C(2)-P-Mn(1)
C(1A)-P-Mn(1)
C(8)-P-Mn(1)
P-Mn(1)-Mn(2)
C(3)-C(2)-P
C(2)-C(3)
C(3)-C(3A)
C(3A)-C(1A)
P-Mn(1)
C(3)-C(3A)
C(3A)-C(1A)
Ta ble 8. Selected Dista n ces (Å) a n d An gles (d eg)
for 25
Mn(1)-Mn(2)
C(2)-C(3)-C(3A)
C(1A)-C(3A)-C(3)
C(3A)-C(1A)-P
118.7(4)
109.0(4)
111.5(3)
P-O
1.4698(13)
1.8067(16)
1.8149(19)
1.8183(18)
1.498(2)
O-P-C(8)
O-P-C(3)
C(8)-P-C(3)
O-P-C(1)
C(8)-P-C(1)
C(3)-P-C(1)
C(1A)-C(1)-P
C(3A)-C(1A)-C(1)
C(3A)-C(3)-P
C(1A)-C(3A)-C(3)
111.76(8)
118.81(9)
106.45(8)
117.90(9)
105.36(8)
94.53(8)
104.20(11)
116.23(15)
104.12(12)
115.96(15)
P-C(8)
P-C(3)
P-C(1)
C(1)-C(1A)
C(1A)-C(3A)
C(3)-C(3A)
dolyl)Mn(CO)3, the only crystallographically character-
ized nitrogen analogue of 19.41 The crystal structure of
unsubstituted (η5-indenyl)Mn(CO)3 is not known.
A thermal ellipsoid plot of 25 is presented in Figure
6, and selected bond distances and angles are sum-
marized in Table 8. The eight carbon atoms of the
heterocycle form a planar fragment. The phosphorus
atom is displaced by 0.48 Å out of this plane, creating a
folding angle of 22.6° with the C(1)-P-C(3) plane. The
P-C bonds within the five-membered ring are similar
1.348(2)
1.504(2)
to those in 11 and 13 (P-C(1) ) 1.8183(18) Å, P-C(3)
) 1.8149(19) Å).
A thermal ellipsoid plot of 26 is depicted in Figure 7,
and selected bond distances and angles are presented
in Table 9. The crystal lattice consists of two indepen-
dent molecules per asymmetric unit, differing only in
the folding angle of the five-membered ring. As with 25,
the eight carbon atoms of the heterocycle form a planar
(40) Plenio, H.; Burth, D. Organometallics 1996, 15, 1151.
(41) J effreys; J . A. D.; Metters, C. J . Chem. Soc., Dalton Trans. 1997,
1624.

3690 Organometallics, Vol. 23, No. 15, 2004
Decken et al.
2.2214(14) Å, Mn(1)-C(3A) ) 2.2255(14) Å), but the
effect is not as prominent as in 19. The Mn-P distances
(2.3696(5) and 2.3725(5) Å) as well as the distances
between the centroids of the five-membered ring and
the metal atoms (1.794 Å for both molecules) compare
favorably to that in 19. The orientation of the Mn(CO)3
tripod and the Mn-CO distances are the same as in
19. The similarities between 19 and 33 are further
manifested by their respective unit cell parameters,
which are virtually identical. The molecular geometry
of 33 also compares favorably with that of its recently
reported ionic triphenylphosphonio derivative.34a
Su m m a r y
A large-scale synthesis for 1-phenylphosphindole and
its conversion to bis(1,1′-phosphindolyl) and the phos-
phindolide anion are reported. These compounds have
been employed in the synthesis of [(µ2-BP)Fe2Cp2-
(CO)4]X (X ) Br, I) and (µ2-BP)2Fe2Cp2(CO)2, where the
BP ligand forms σ-bonds, bridging two metal centers
and (BP-Ph)Mn2(CO)9, in which the ligand acts as a
phosphine. (BP-Ph)Mn2(CO)9 was reacted with organic
and organometallic radicals to give the π-complex (η5-
BP)Mn(CO)3. Attempts to isolate 2-phenyl-iso-phosphin-
dole failed due to its high reactivity, resulting in
spontaneous and irreversible polymerization. These
problems were avoided through the synthesis of 2-phen-
yl-4,7-dihydro-iso-phosphindole, which was employed in
the preparation of (η5-iBP-H2)Mn(CO)3. Dehydrogena-
tion of (η5-iBP-H2)Mn(CO)3 yielded (η5-iBP)Mn(CO)3, the
first metal complex of the hitherto unknown iBP ligand.
F igu r e 8. View of one of the independent molecules of 33
showing the atom-numbering scheme. Thermal ellipsoids
are at the 30% probability level.
Ta ble 9. Selected Dista n ces (Å) a n d An gles (d eg)
for On e of th e In d ep en d en t Molecu les of 26
P(1)-O(1)
P(1)-C(8)
P(1)-C(3)
P(1)-C(1)
C(1)-C(1A)
C(1A)-C(3A)
C(3)-C(3A)
1.4852(10)
1.7980(13)
1.8083(13)
1.8147(14)
1.5112(18)
1.3950(18)
1.5046(17)
O(1)-P(1)-C(8)
O(1)-P(1)-C(3)
C(8)-P(1)-C(3)
O(1)-P(1)-C(1)
C(8)-P(1)-C(1)
C(3)-P(1)-C(1)
C(1A)-C(1)-P(1)
C(3A)-C(1A)-C(1)
C(3A)-C(3)-P(1)
C(1A)-C(3A)-C(3)
111.07(6)
115.00(6)
110.00(6)
113.82(6)
112.08(6)
93.84(6)
102.25(9)
114.47(11)
102.59(8)
114.56(11)
Ta ble 10. Selected Dista n ces (Å) a n d An gles (d eg)
for On e of th e In d ep en d en t Molecu les of 33
Mn(1)-C(1)
Mn(1)-C(3)
Mn(1)-C(1A)
Mn(1)-C(3A)
Mn(1)-P(1)
Mn(1)-C(10)
Mn(1)-C(8)
Mn(1)-C(9)
P(1)-C(1)
2.1555(16)
2.1693(16)
2.2214(14)
2.2255(14)
2.3696(5)
1.7885(17)
1.7983(16)
1.8032(17)
1.7583(19)
1.7594(18)
1.426(2)
C(1)-P(1)-C(3)
89.46(8)
C(1)-C(1A)-C(3A)
C(1A)-C(1)-P(1)
C(3A)-C(3)-P(1)
C(3)-C(3A)-C(1A)
111.42(14)
113.54(12)
113.48(12)
111.62(14)
Exp er im en ta l Section
Gen er a l Con sid er a tion s. All reactions were carried out
under an inert atmosphere of argon using standard Schlenk
techniques unless otherwise noted. Solvents were dried and
distilled according to standard procedures42 or directly ob-
tained form a J C Meyer solvent purification system. Organic
solvents were degassed using freeze-thaw techniques, and
aqueous solutions were purged with argon prior to use. Melting
points were measured in open glass capillaries using a
Gallenkamp melting point apparatus and were uncorrected.
1H and 13C NMR spectra were recorded on a Varian Unity 400
spectrometer at 399.99 and 100.6 MHz, respectively, and
referenced relative to the residual solvent signal. 31P NMR
spectra were obtained at 161.89 MHz and were recorded
relative to external triphenylphosphine (δ ) -6.0 ppm).
Electron impact (EI) and fast atom bombardment (FAB)+ MS
were performed on a Kratos MS-50 mass spectrometer. Helium
was used as the bombarding gas. Infrared spectra were
obtained on a Bruker IFS 25 instrument using KBr disks.
Unless otherwise stated, all reagents were obtained from
commercial suppliers and used without purification. Com-
pounds 4,26 10,24,25 26,33 FeCp(CO)2I,43 and FeCp(CO)2Br44 were
prepared according to literature procedures. Flash chroma-
tography was carried out using Merck silica gel (330-400
mesh). Microanalyses were performed by Galbraith Labora-
tories in Knoxville, TN.
P(1)-C(3)
C(1A)-C(1)
C(1A)-C(3A)
C(3)-C(3A)
1.430(2)
1.424(2)
fragment. The displacement of the phosphorus atom is
much more pronounced than in 25 (0.66 Å for P(1) and
0.61 Å for P(2)), creating a folding angle of 32.9° and
30.0° with the C(1)-P(1)-C(3) or C(11)-P(2)-C(13)
plane, respectively. The P-C bonds within the hetero-
cycle are similar to those in 11, 13, and 25, ranging from
1.8083(13) Å (P(1)-C(3)) to 1.8147(14) Å (P(1)-C(1)).
A thermal ellipsoid plot of 33 is shown in Figure 8,
and selected bond distances and angles are presented
in Table 10. Complex 33 crystallizes with two indepen-
dent molecules per asymmetric unit that have identical
metric parameters within experimental error. The
ligand is planar in each case, and a very high degree of
bond delocalization is observed. The variation of bond
length between the four carbon atoms of the five-
membered ring is marginal, ranging from 1.424(2) Å
(C(3)-C(3A)) to 1.430(2) Å (C(1A)-C(3A)) and are
significantly less that those found for 19. As with 19,
the metal is slightly displaced away from C(1A)/C(3A),
and the metal-C distances consist of a pair of short
bonds (Mn(1)-C(1) ) 2.1555(16) Å, Mn(1)-C(3) )
2.1693(16) Å) and a pair of long bonds (Mn(1)-C(1A) )
P r ep a r a t ion of 2-Tr im et h ylsilyl-1-p h en ylp h osp h in -
d ole Oxid e (11). N-Butyllithium (240 mL, 2.5 M in hexanes,
600 mmol) was added to a solution of 10 (55.6 g, 218 mmol) in
ether (2000 mL) at 0 °C. The yellow solution was stirred at
(42) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of
Laboratory Chemicals; Pergamon Press: New York, 1980.
(43) King, R. B.; Stone, G. Inorg. Synth. 1963, 7, 110.
(44) Hallam, B. F.; Pauson, P. L. J . Chem. Soc. 1956, 3030.

Organometallic Benzannelated Phospholyl Complexes
Organometallics, Vol. 23, No. 15, 2004 3691
room temperature for 2.5 h. A solution of PhPCl2 (43 mL, 313
mmol) in ether (500 mL) was added dropwise at 0 °C over a
period of 1 h. The orange suspension was stirred at room
temperature for 20 h, followed by addition of ether (5000 mL)
and saturated aqueous NaHCO3 (500 mL) while the apparatus
was open to the air. The mixture was stirred until all of the
solids had dissolved and the layers were separated. The yellow
organic phase was washed with saturated aqueous NaCl (500
mL), dried over Na2SO4, and filtered, and the solvent was
evaporated under reduced pressure to give a wet yellow solid.
Hexane (30 mL) was added, and the solid filtered under suction
and washed with hexane (2 × 30 mL) to give 11 (51.9 g, 174
mmol, 80%) as a yellow solid. Mp: 135-136 °C. 1H NMR
(acetone-d6): δ 7.86 (s, 1H); 7.70-7.39 (m, 9H); 0.09 (s, 9H).
13C NMR (acetone-d6): δ 152.9 (d, J P-C 7 Hz); 144.3 (d, J P-C
37 Hz); 142.5 (d, J P-C 59 Hz); 137.0 (d, J P-C 100 Hz); 133.8;
132.8; 132.5 (d, J P-C 95 Hz); 131.6 (d, J P-C 10 Hz); 130.5 (d,
(20 mL). The crude product solution can be used without
further purification. Isolation of 14 was accomplished by
filtration of the solution through a sintered glass funnel and
removal of the solvent under reduced pressure to give 14 as a
yellow oil. An inseparable mixture of diastereomers (meso and
racemic) was obtained.32b 1H NMR (CDCl3): δ 7.80-6.15 (m).
31P{1H} NMR (CDCl3): δ -19, -24 ppm. MS (EI, m/z (%),
assignment): 266 (36) {C16H12P2}+ {(C8H6P)2}+; 133 (100)
{C8H6P}+.
P r ep a r a tion of [(µ2-P h osp h in d olyl)F e2Cp 2(CO)4]I (15).
A solution of 4 (10 mL, 0.2 M in THF, 2 mmol) was cooled to
0 °C, and AlCl3 (0.089 g, 0.67 mmol) was added. After stirring
at 0 °C for 30 min, FeCp(CO)2I (1.215 g, 4 mmol) was added,
producing a red-brown solution with a solid precipitate. The
solid was isolated by filtration, washed with hexane, and dried
under reduced pressure to give 0.60 g (0.98 mmol, 49%) of 15
as an orange powder. Anal. Found: C, 42.54; H, 3.26. Calcd
for C22H16PFe2O4Br: C, 43.04; H, 2.63. Mp: 179 °C (dec). 1H
NMR (acetone-d6): δ 7.92 (dd, 7.2 Hz, J P-H 7.2 Hz, 1H); 7.79
(d, 7.2 Hz, 1H); 7.64 (dd, 7.6 Hz, J P-H 40.0 Hz, 1H); 7.54-7.45
J
P-C 10 Hz); 129.7 (d, J P-C 12 Hz); 129.2 (d, J P-C 10 Hz); 125.7
(d, J P-C 11 Hz); -0.8. 31P{1H} NMR (acetone-d6): δ 45 ppm.
MS (EI, m/z (%), assignment): 298 (42) {C17H19OPSi}+ {C8H5-
(SiMe3)P(O)Ph}+; 282 (100) {C17H19PSi}+ {C8H5(SiMe3)P-
(Ph)}+; 226 (40) {C14H11OP}+ {(C8H6P)(O)(Ph)}+; 221 (23)
{C11H14OPSi}+ {C8H5(SiMe3)P(O)}+; 210 (36) {C14H11P}+
{(C8H6P)(Ph)}+; 149 (40) {(C8H6P)(O)}+; 133 (41) {C8H6P}+; 77
(81) {C6H5}+; 73 (51) {C3H9Si}+.
(m, 2H); 7.33 (dd, 7.4 Hz, J P-H 27.4 Hz, 1H); 5.46 (s, 10H). 13
C
NMR (acetone-d6): δ 212.5 (d, J P-C 19 Hz, CO); 211.8 (d, J P-C
19 Hz, CO); 153.3 (d, J P-C 28 Hz); 145.6 (d, J P-C 20 Hz); 141.3
(d, J P-C 13 Hz); 133.4; 130.7; 128.9 (d, J P-C 14 Hz); 128.3 (d,
J
P-C 10 Hz); 126.5 (d, J P-C 6 Hz); 88.9. 31P{1H} NMR (acetone-
d6): δ 37 ppm. IR: νCO 2044 (vs); 2032 (vs); 1999 (vs); 1978
(s). MS (EI, m/z (%), assignment): 375 (30) {C18H16PFe2}+
{(C8H6P)Fe2Cp2}+; 310 (76) {C13H11PFe2}+ {(C8H6P)Fe2Cp}+;
254 (100) {C13H11PFe}+ {(C8H6P)FeCp}+; 186 (87) {C10H10Fe}+
{FeCp2}+; 133 (88) {C8H6P}+; 120 (25) {C5H5Fe}+ {FeCp}+; 56
(88) {Fe}+.
P r epar ation of 1-P h en ylph osph in dole Oxide (12). TBAF
(331 mL, 1.0 M in THF, 331 mmol) was added to a solution of
11 (51.9 g, 174 mmol) in THF (174 mL) and the dark brown
solution heated to reflux for 4 h. The mixture was cooled to
room temperature, followed by addition of ether (1750 mL) and
saturated aqueous NaHCO3 (300 mL), while the apparatus was
open to the air. The mixture was stirred for 20 min, and the
layers were separated. The yellow organic phase was washed
with saturated aqueous NaCl (300 mL), dried over Na2SO4,
and filtered, and the solvent was evaporated under reduced
pressure to give 12 as a brown oil (19.7, 87 mmol, 50%). The
crude product was used without further purification. 1H NMR
(acetone-d6): δ 7.90-7.10 (m, 9H); 7.01 (dd, 3.1 Hz, J P-H 16.2
Hz, 1H); 6.55 (dd, 3.5 Hz, J P-H 10.5 Hz, 1H). 13C NMR (acetone-
d6): δ 146.1 (d, J P-C 12 Hz); 143.1 (d, J P-C 31 Hz); 133.9 (d,
J P-C 2 Hz); 133.1 (d, J P-C 3 Hz); 131.6 (d, J P-C 10 Hz); 130.5
(d, J P-C 10 Hz); 129.8 (d, J P-C 12 Hz); 129.4 (d, J P-C 10 Hz);
128.6; 127.7; 126.0 (d, J P-C 10 Hz). 31P {1H} NMR (acetone-
P r epar ation of [(µ2-P h osph in dolyl)Fe2Cp2(CO)4]Br (16).
In analogy with the preparation of 15, reaction of 4 (10 mL,
0.1 M in THF, 1 mmol) and FeCp(CO)2Br (0.514 g, 2 mmol)
1
gave 0.42 g (0.74 mmol, 74%) of 16 as an orange powder. H
NMR, 13C NMR, 31P NMR, and MS were identical to that of
15.
P r ep a r a tion of (µ2-P h osp h in d olyl)2F e2Cp 2(CO)2 (17).
To a solution of 14 in toluene, as obtained above, was added
Fe2Cp2(CO)4 (0.354 g, 1 mmol), and the mixture was heated
to reflux for 1 h to give a dark red-brown suspension. The
solvent was evaporated under reduced pressure and the red-
brown solid purified by flash chromatography using toluene
to give 17 (0.125 g, 222 mmol, 22%) as a green solid. Four
inseparable isomers were obtained. Their 1H NMR and 13C
NMR data was complicated due to multiple peak overlaps and
d6): δ 37 ppm. MS (EI, m/z (%), assignment): 226 (67) {C14H11
-
OP}+ {(C8H6P)(O)(Ph)}+; 210 (39) {C14H11P}+ {(C8H6P)(Ph)}+;
133 (30) {C8H6P}+; 77 (51) {C6H5}+.
1
P r ep a r a tion of 1-P h en ylp h osp h in d ole (13). Compound
13 was prepared using a modified literature procedure.24-26
SiHCl3 (17.6 mL, 174 mmol) was added to a solution of 12 (19.7
g, 87 mmol) in toluene (1750 mL), and the yellow solution was
heated to reflux for 1.5 h. The mixture was cooled to 0 °C and
hydrolyzed with 2 M NaOH (320 mL), and the layers were
separated quickly while the apparatus was open to the air.
The yellow organic phase was dried over Na2SO4 and filtered,
and the solvent evaporated under reduced pressure to give a
yellow-brown oil. The product was crystallized from methanol
to give 13 (9.2 g, 44 mmol, 50%) as a yellow solid. Mp: 60-62
°C. 1H NMR (acetone-d6): δ 7.70 (dd, 4.3 Hz, J P-H 11.8 Hz,
1H); 7.66 (d, 7.6 Hz, 1H); 7.48-7.25 (m, 8H); 7.01 (dd, 7.6 Hz,
are reported for the Cp region only. Mp: 195 °C (dec). H NMR
(C6D6): δ 3.82 (s); 3.73 (s); 3.66 (s); 3.57 (s); 3.52 (s). 13C NMR
(C6D6): δ 81.1, 80.6, 80.3, 80.1, 79.9. 31P{1H} NMR (C6D6): δ
-26 (d, J P-P 248.2 Hz); -31; -38 (d, J P-P 248.2 Hz); -40; -41.
IR: νCO 2044 (vs); 2032 (vs); 1999 (vs); 1978 (s). MS (EI, m/z
(%), assignment): 564 (71) {C28H22P2Fe2O2}+ {(C8H6P)2Fe2Cp2-
(CO)2}+; 536 (69) {C27H22P2Fe2O}+ {(C8H6P)2Fe2Cp2(CO)}+; 508
(82) {C26H22P2Fe2}+ {(C8H6P)2Fe2Cp2}+; 375 (62) {C18H16PFe2}+
{(C8H6P)Fe2Cp2}+; 310 (77) {C13H11PFe2}+ {(C8H6P)Fe2Cp}+;
254 (100) {C13H11PFe}+ {(C8H6P)FeCp}+; 186 (83) {C10H10Fe}+
{FeCp2}+; 133 (81) {C8H6P}+; 121 (89) {C5H5Fe}+ {FeCp}+; 56
(79) {Fe}+.
P r ep a r a tion of 1-P h en ylp h osp h in d ole Dim a n ga n ese
Non a ca r bon yl (18). A solution of 13 (1.05 g, 5 mmol) in
xylenes (20 mL) was added to a solution of Mn2(CO)10 (1.95 g,
5 mmol) in xylenes (30 mL). The resultant orange solution was
heated to reflux for 12 min to give an orange suspension. The
mixture was cooled to room temperature and filtered through
a sintered glass funnel, producing a red-orange solution. The
solvent was evaporated under reduced pressure and the red-
orange oil purified by flash chromatography using a 4:1
mixture of hexanes/ether to give 18 (1.45 g, 2.5 mmol, 51%)
as a red-orange oil. Anal. Found: C, 48.05; H, 1.94. Calcd for
J P-H 39.6 Hz, 1H). 13C NMR (acetone-d6): δ 145.6 (d, J P-C
6
Hz); 143.8; 139.2; 134.3 (d, J P-C 10 Hz); 133.2 (d, J P-C 15 Hz);
132.6 (d, J P-C 19 Hz); 129.3; 128.9 (d, J P-C 20 Hz); 128.7 (d,
J P-C 8 Hz); 128.1; 126.1 (d, J P-C 7 Hz); 124.2. 31P{1H} NMR
(acetone-d6): δ 0 ppm. MS (EI, m/z (%), assignment): 210 (20)
{C14H11P}+ {(C8H6P)(Ph)}+; 133 (68) {C8H6P}+; 77 (72) {C6H5}+.
P r ep a r a tion of Bis(1,1′-p h osp h in d olyl) (14). A solution
of 4 (10 mL, 0.2 M in THF, 2 mmol) was cooled to 0 °C, and
AlCl3 (0.089 g, 0.67 mmol) was added. The mixture was stirred
at 0 °C for 30 min, and I2 (0.305 g, 1.2 mmol) was added to
give a light yellow-brown suspension. The solvent was removed
under reduced pressure, and the oil was dissolved in toluene
C
21H11PMn2O9: C, 48.28; H, 1.94. Mp: 140 °C. 1H NMR
(acetone-d6): δ 8.18 (ddd, 4.0 Hz, 7.0 Hz, J P-H 12.6 Hz, 1H);

3692 Organometallics, Vol. 23, No. 15, 2004
Decken et al.
short path distillation head, 100 mL receiving flask, and 500
mL vacuum ballast. The pressure was adjusted to ∼100 mmHg
using a partially opened valve connecting a water aspirator
and a three-way valve, which was connected to a Hg manom-
eter and the vacuum adapter of the pyrolysis apparatus. The
reaction flask was heated to ∼100-120 °C in a sand bath, and
the receiving flask was cooled in an acetone/LN2 bath. At the
onset of pyrolysis, the highly viscous mixture released large
quantities of gases, followed by a rapid decrease in viscosity.
After completion of the reaction, water (6.7 mL) was added to
the pyrolysate and the two layers were separated. The organic
layer was washed with water (2 × 2.2 mL), cold 5% HCl (2.2
mL), saturated NaHCO3 (2.2 mL), and saturated NaCl (2.2
mL). The crude product was dried over 4 Å molecular sieves
for 20 min and decanted to give 23 (0.312 g, 2.94 mmol, 10%)
as a colorless liquid, used immediately in the preparation of
24.
Sch em e 7
7.80 (dd, 2.0 Hz, J P-H 11.6 Hz, 1H); 7.78 (dd, 1.2 Hz, J P-H 11.6
Hz, 1H); 7.75-7.71 (m, 1H); 7.64-7.59 (m, 3H); 7.48 (dd, 8.0
Hz, J P-H 65 Hz, 1H); 7.51-7.48 (m, 3H). 13C NMR (acetone-
d6): δ 223.8 (br, CO); 143.5 (d, J P-C 17 Hz); 141.1 (d, J P-C
Hz); 141.2 (d, J P-C 50 Hz); 134.5 (d, J P-C 42 Hz); 133.3 (d, J P-C
43 Hz); 132.2 (d, J P-C 2 Hz); 131.5 (d, J P-C 2 Hz); 131.3 (d,
2
Ch a r a cter iza tion of 37. 1H NMR (CDCl3): δ 5.72 (s, 2H);
3.68 (d, J 12 Hz, 2H); 3.28 (s, 6H); 3.18 (s, 6H); 3.06 (d, J 12
Hz, 2H); 2.90 (s, 2H); 2.52 (d, J 18 Hz, 2H); 1.94 (d, J 18 Hz,
2H). 13C NMR (CDC13): δ 126.3 (s); 72.6 (s); 60.4 (s); 58.9 (s);
31.3 (s); 30.9 (s). MS (EI, m/z (%) assignment): 228 (26)
{C12H24N202}+.
J
P-C 10 Hz); 130.5 (d, J P-C 13 Hz); 130.2 (d, J P-C 10 Hz); 129.5
(d, J P-C 10 Hz); 126.5 (d, J P-C 6 Hz). 31P{1H} NMR (acetone-
d6): δ 73 ppm. IR: νCO 1922 (s); 1944 (s); 1968 (s); 1992 (s);
2018 (s); 2090 (m). MS (EI, m/z (%), assignment): 460 (5)
{C19H11PMn2O5}+ {(C8H6P)(Ph)Mn2(CO)5}+; 432 (23) {C18H11
-
PMn2O4}+ {(C8H6P)(Ph)Mn2(CO)4}+; 377 (20) {C18H11PMnO4}+
{(C8H6P)(Ph)Mn(CO)4}+; 349 (18) {C17H11PMnO3}+ {(C8H6P)-
(Ph)Mn(CO)3}+; 321 (15) {C16H11PMnO2}+ {(C8H6P)(Ph)Mn-
(CO)2}+; 293 (10) {C15H11PMnO}+ {(C8H6P)(Ph)Mn(CO)}+; 266
(22) {C16H12P2}+ {(C8H6P)2}+; 265 (25) {C14H11PMn}+ {(C8H6P)-
(Ph)Mn}+; 244 (23) {C10H6PMnO2}+ {(C8H6P)Mn(CO)2}+; 216
(30) {C9H6PMnO}+ {(C8H6P)Mn(CO)}+; 210 (54) {C14H11P}+
{(C8H6P)(Ph)}+; 188 (30) {(C8H6P)Mn}+; 149 (100) {(C8H6P)-
(O)}+; 133 (22) {C8H6P}+; 77 (26) {C6H5}+.
P r ep a r a tion of 2-P h en yl-1,3,4,7-tetr a h yd r o-iso-p h os-
p h in d olen iu m Ch lor id e (24). Compound 24 was prepared
according to a modified literature procedure.33 Under exclusion
of light, PhPCl2 (0.44 mL, 327 mmol) was added to a mixture
of freshly prepared 23 (0.312 g, 2.94 mmol) and BHT (0.004
g) in ligroin (1.6 mL). The mixture was allowed to stand at
room temperature for 5 days, producing a pale yellow solid
precipitate. The solid was isolated by filtration and washed
with hexane (3 × 0.5 mL) to give 24 (0.674 g, 2.38 mmol, 81%)
as a pale yellow fine solid, used immediately in the preparation
of 25 and 31. 1H NMR (CD2Cl2): δ 8.08 (dd, J 7.2 Hz, J P-H
17.1 Hz, 2H); 7.60-7.72 (m, 3H); 5.84 (s, 2H); 4.05 (d, J P-H
8.7 Hz, 4H); 2.96 (s, 4H). 31P{1H} NMR (CD2Cl2): δ 42.7.
P r ep a r a tion of 2-P h en yl-1,3,4,7-tetr a h yd r o-iso-p h os-
p h in d ole 2-Oxid e (25). Compound 25 was prepared using a
modified literature procedure.33 24 (0.674 g, 2.38 mmol) was
added to a saturated NaHCO3 solution (2.14 mL) at 0 °C,
forming an insoluble oil. The resulting mixture was extracted
with CHCl3 (6 × 1.1 mL), and the organic phases were
combined, dried over Na2SO4, filtered, and concentrated under
reduced pressure to give 25 (0.262 g, 1.14 mmol, 48%) as a
pale yellow solid. The 1H, 13C, and 31P NMR matched the
reported literature data.33
P r ep a r a tion of η5-P h osp h in d ole Ma n ga n ese Tr ica r -
bon yl (19). Compound 19 was prepared using a modified
literature procedure.26 A solution of 13 (1.05 g, 5 mmol) in
xylenes (20 mL) was added to a solution of Mn2(CO)10 (1.95 g,
5 mmol) in xylenes (30 mL), and the resultant orange solution
was heated to reflux for 3 h to give a dark red-brown
suspension. The mixture was cooled to room temperature and
filtered through a sintered glass funnel, producing a dark red
solution. The solvent was evaporated under reduced pressure
and the red oil purified by flash chromatography using hexanes
to give 19 (0.230 g, 0.85 mmol, 17%) as a red solid. 31P{1H}
NMR (acetone-d6): δ -53 ppm. 1H NMR, MS, and IR matched
the reported literature data.26
P r ep a r a tion of η5-P h osp h in d ole Ma n ga n ese Tr ica r -
bon yl (19) via 18. Procedure A: A solution of 18 (0.1 g, 0.175
mmol) and Mn2(CO)10 (0.068 g, 0.175 mmol) in xylenes (7 mL)
was heated to reflux for 2 h to give 19, the only product
containing phosphorus as determined by in situ 31P NMR.
Procedure B: A solution of 18 (0.075 g, 0.138 mmol) and
TEMPO (0.022 g, 0.138 mmol) in xylenes (5.5 mL) was heated
to reflux for 2 h to give 19, the only product containing
phosphorus as determined by in situ 31P NMR.
P r ep a r a tion of 4,5-Dim eth ylen ecycloh exen e (23). 23
was prepared using a modified literature procedure (see
Scheme 7).33 Ca u tion : Pyrolysis of 37 can lead to explosions,
and for safety reasons the scale was decreased and the
synthesis carried out as follows. A solution of 36 (23.03 g, 117
mmol) in methanol (49.2 mL) was cooled to 0 °C, and H2O2
(32.8 mL, 30% solution in water, 289 mmol) was added,
followed by a second portion (32.8 mL, 30% solution in water,
289 mmol) 3 h later. The solution was stirred for 36 h at room
temperature, after which the pH was neutral as indicated by
pH paper. Excess H2O2 was destroyed by stirring the reaction
mixture with Pt/C (30 mg), until the evolution of oxygen ceased
(48 h). The solid precipitate was removed by filtration and the
filtrate concentrated under reduced pressure to give 37 (7 g,
31 mmol, 26%) as a clear highly viscous pale yellow oil. The
crude material and hydroquinone (0.020 g) were added to a
pyrolysis apparatus, consisting of a 100 mL reaction flask,
P r ep a r a tion of 2-P h en yl-iso-p h osp h in d olin e (27). To
a solution of 26 (0.347 g, 1.52 mmol) in toluene (31 mL) was
added HSiCl3 (0.31 mL, 3.04 mmol) and the resulting clear
solution heated to reflux for 1.5 h. The mixture was cooled to
room temperature and quenched with 2 M NaOH (5.6 mL).
The organic layer was separated, washed with a saturated Na2-
CO3 solution (2.0 mL), dried over Na2SO4, filtered, and
concentrated under reduced pressure to give 27 (0.297 g, 1.40
1
mmol, 92%) as a colorless oil. H NMR (C6D6): δ 7.31 (s, 2H);
6.97 (m, 7H); 3.19 (m, 2H); 2.96 (d, J P-H 17.2 Hz, 2H). 13C NMR
(C6D6): δ 142.1 (s); 141.2 (s); 136.6 (d, J P-H 4.6 Hz); 131.66
(s); 128.6 (d, J P-H 9.6 Hz); 127.0 (s); 126.65 (s); 32.7 (d, 495
Hz). 31P{1H} NMR (C6D6): δ -14.0. MS (EI, m/z (%) assign-
+
ment): 212 (76) {C14H13P}+ {C8H8PPh}+; 181 (19) {C14H13
}
{C8H8Ph}+; 135 (39) {C8H8P}+; 104 (36) {C8H8}+; 77 (23)
{C6H5}+.
P r ep a r a tion of 2-Br om o-2-p h en yl-iso-p h osp h in d ole-
n iu m Br om id e (28). To a solution of 27 (0.078 g, 0.368 mmol)
in CH2Cl2 (2.0 mL) was added Br2 (6.75 mL, 0.109 M in CH2-
Cl2, 0.735 mmol) to give a dark orange solution. The mixture
was concentrated under reduced pressure to give an orange
oil, which was dissolved in CH2Cl2 (2.0 mL) and added slowly
to hexane (30 mL) to give an orange solid precipitate. The pale
orange supernatant was decanted and the solid dried under
high vacuum for 5 min to give 28 (0.107 g, 0.288 mmol, 78%)

Organometallic Benzannelated Phospholyl Complexes
Organometallics, Vol. 23, No. 15, 2004 3693
as an orange solid. 1H NMR (CD2Cl2): δ 7.75 (m, 3H); 7.58
(m, 2H); 7.37 (m, 4H); 3.72 (m, 4H). 13C NMR (CD2Cl2): δ 134.6
(s); 133.2 (d, J P-C 9.65 Hz); 130.5 (d, J P-C 10.46 Hz); 129.8 (d,
J P-C 12.77 Hz); 129.1 (s); 127.8 (d, J P-C 15.99 Hz); 125.0 (d,
J P-C 79.38 Hz); 34.2 (d, J P-C 67.27 Hz). 31P{1H} NMR (CD2-
Cl2): δ 74.4. IR: 3054 (w); 2958 (m); 2900 (w); 1264 (s); 1180
PO9Mn2}+ {(C8H8PPh)Mn2(CO)9}+; 462 (5) {C19H13PO5Mn2}+
{(C8H8PPh)Mn2(CO)5}+; 434 (5 {C18H13PO4Mn2}+ {(C8H8PPh)-
Mn2(CO)4}+; 406 (2) {C17H13PO3Mn2}+ {(C8H8PPh)Mn2(CO)3}+;
379 (25) {C18H13PO4Mn}+ {(C8H8PPh)Mn(CO)4}+; 351 (5)
{C17H13PO3Mn}+ {(C8H8PPh)Mn(CO)3}+; 323 (4) {C16H13PO2-
Mn}+ {(C8H8PPh)Mn(CO)2}+; 295 (2) {C15H13POMn}+ {(C8H8-
PPh)Mn(CO)}+; 267 (100) {C14H13PMn}+ {(C8H8PPh)Mn}+; 212
(38) {C14H13P}+ {C8H8PPh}+. HRMS (EI, m/z): {C23H13PO9-
Mn2}+ calcd 573.90582, found 573.90788.
(m); 1086 (vs); 1026 (s); 920 (m); 802 (vs); 742 (s); 694 (m) cm-1
.
Deh yd r obr om in a tion of 2-Br om o-2-p h en yl-iso-p h os-
p h in d olen iu m Br om id e (28). To a solution of 28 (0.020 g,
0.054 mmol) in CH2Cl2 (5 mL) was added NEt3 (0.04 mL, 0.288
mmol) dropwise. The orange solution slowly changed color to
pale brown, and a pale brown solid precipitate was formed.
The solid was isolated by filtration and found to be insoluble
in all organic solvents. The mother liquor gave no signal in
the 31P NMR spectrum. The solvent was evaporated under
P r ep a r a tion of (η5-iso-P h osp h in d olyl) Ma n ga n ese Tr i-
ca r bon yl (33). An orange solution of 32 (0.163 g, 0.595 mmol)
in benzene (15.5 mL) was added to DDQ (0.155 g, 0.681 mmol).
The resulting orange mixture was heated to reflux overnight,
producing a dark solid precipitate. The solid was filtered and
washed with benzene (3 × 2 mL). The combined organic phases
were concentrated under reduced pressure to yield a red oil.
Hexane (3 × 2 mL) was added, and the resulting brown solid
was removed by filtration to give a yellow solution. The
solution was concentrated under reduced pressure to give a
yellow oil. The oil was purified by sublimation (0.140 mmHg,
25 °C) onto a coldfinger (12 °C) to give 33 (0.051 g, 0.188 mmol,
1
reduced pressure and the solid identified as HNEt3Br. The H
NMR matched the reported literature data. Anal. Found: C,
39.00; H, 7.79. Anal. Calcd for C6H16NBr: C, 39.57; H, 7.69.
P r ep a r a tion of 2-P h en yl-4,7-d ih yd r o-iso-p h osp h in d ole
(31). To a colorless solution of 24 (0.169 g, 0.59 mmol) in CH2-
Cl2 (5 mL) was added NEt3 (0.18 mL, 1.27 mmol), resulting in
immediate formation of a white vapor and a yellow solution.
HCl (3 M, 0.13 mL) was added, the layers were separated, and
the yellow organic phase was washed with H2O until the pH
of the aqueous phase was neutral (3 × 0.5 mL). The pale yellow
organic phase was dried over Na2SO4, filtered, and concen-
trated under reduced pressure to give a colorless oil. Hexane
(0.5 mL) was added, resulting in a colorless solid and a
colorless solution. The solution was filtered and concentrated
under reduced pressure to give 31 (0.0567 g, 0.267 mmol, 45%)
1
32%) as a yellow solid. H NMR (CD2Cl2): δ 7.50 (dd, J 2.95
Hz, J P-H 6.71 Hz, 2H); 7.27 (dd, J 2.95 Hz, J P-H 6.71 Hz 2H);
5.19 (d, J P-H 35.2 Hz, 2H). 13C NMR (CD2Cl2): δ 223.1 (s, br);
127.1 (s); 126.0 (s); 112.8 (d, J P-C 7.24 Hz); 86.4 (d, J P-C 64.2
Hz). 31P (CH2Cl2): δ -1.5 (t, J P-H 34.3 Hz). IR: νCO 2019 (s),
1939 (s, br) cm-1. MS (EI, m/z (%), assignment): 272 (26)
{C11H6PO3Mn}+ {(C8H6P)Mn(CO)3}+; 216 (44) {C9H6POMn}+
{(C8H6P)Mn(CO)}+; 188 (100) {C8H6PMn}+ {C8H6PMn}+. EI
HRMS (m/z): {C11H6PO3Mn}+ calcd 271.94351, found
271.94352.
1
as a colorless oil. H NMR (CD2Cl2): δ 7.41 (m, 2H); 7.33 (m,
3H); 6.61 (d, J
38.1 Hz, 2H); 5.93 (s, 2H); 3.34 (d, J P-H 3.3
PH
X-r a y Diffr a ction Exp er im en ts. Crystals suitable for
diffraction studies were grown by solvent evaporation using
CH2Cl2 (25, 26) or hexane (18) at 25 °C, by solvent diffusion
using acetone/pentane (15) at -25 °C, or by sublimation at
0.140 mmHg at 25 °C onto a coldfinger at 12 °C (33, 19). Single
crystals were coated with Paratone-N oil, mounted using a
glass fiber, and frozen in the cold nitrogen stream of the
goniometer. A hemisphere of data was collected on a Bruker
AXS P4/SMART 1000 diffractometer using $ and θ scans with
a scan width of 0.3° and 30 s (26, 25, 13, 11), 20 s (15), or 10
s (33, 18) exposure times. The detector distance was 6 cm (25),
5 cm (26, 33), or 4 cm (18, 15, 13, 11). The data were reduced
(SAINT)45 and corrected for absorption (SADABS).46 The
structures were solved by direct methods and refined by full-
matrix least squares on F2 (SHELXTL).47 All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were
found in Fourier difference maps and refined isotropically.
Hz, 4H). 13C NMR (CD2Cl2): δ 146.7 (d, J P-C 8.22 Hz); 133.3
(d, J P-C 18.09 Hz); 131.9 (d, J P-C 10.93 Hz); 129.2 (d, J P-C 1.66
Hz); 128.7 (d, J P-C 8.22 Hz); 128.2 (d, J P-C 1.66 Hz); 124.5 (s);
28.7 (d, J P-C 3.84 Hz). 31P NMR (CH2Cl2): δ 4.2 (t, J P-H 38.1
Hz). IR: 660 (m), 692 (s), 724 (m), 744 (s), 784 (s), 812 (s), 916
(w), 936 (w), 964 (m), 996 (w), 1096 (m), 1116 (w), 1184 (m),
1228(m), 1264 (w), 1304 (w), 1356 (s), 1420 (s), 1436 (s), 1480
(m), 1572 (w), 1584 (w), 1656 (w), 2812 (m), 2872 (w), 3000
(w), 3028 (m), 3048 (w), 3064 (w) cm -1. MS (EI, m/z (%),
assignment): 212 (100) {C14H13P}+ {(C8H8PPh}+; 135 (63)
{C8H8P}+. EI HRMS (m/z): {C14H13P}+ calcd 212.07549, found
212.07475.
P r epar ation of (η5-4,7-Dih ydr o-iso-ph osph in dolyl) Man -
ga n ese Tr ica r bon yl (32) a n d 2-P h en yl-4,7-Dih yd r o-iso-
p h osp h in d ole Dim a n ga n ese Non a ca r bon yl (34). A solu-
tion of 31 (0.8 g, 3.77 mmol) in xylenes (16 mL) was added to
Mn2(CO)10 (0.735 g, 1.88 mmol) in xylenes (16 mL) and the
resulting yellow mixture heated to reflux for 1 h. The reaction
mixture, consisting of a red solution and a dark solid, was
cooled to room temperature and the solvent removed under
reduced pressure to give a red oil with a dark solid. The
mixture was separated by flash chromatography using a 10:1
mixture of hexane/ether to give 32 (0.163 g, 0.595 mmol, 16%)
as an orange oil and trace amounts of 34 as an orange oil.
Ch a r a cter iza tion of 32. 1H NMR (CD2Cl2): δ 5.96 (s, 2H);
4.54 (d, J P-H 35.6 Hz, 2H); 3.31 (d, J 16.0 Hz, 2H); 3.11 (d, J
16.0 Hz,2H). 13C NMR (CD2Cl2): δ 223.7 (s, br); 123.1 (s); 112.1
(d, J P-C 7.24 Hz); 92.2 (d, J P-C 63.4 Hz); 26.6 (s). 31P NMR
(CD2Cl2): δ -35.3 (t, J P-H 35.1 Hz). IR: νCO 2016 (s), 1930 (s,
br) cm-1. MS (EI, m/z (%), assignment): 274 (5) {C11H8PO3-
Mn}+ {(C8H8P)Mn(CO)3}+; 218 (10) {C9H8POMn}+ {(C8H8P)-
Mn(CO)}+; 190 (30) {C8H8PMn}+ {C8H8PMn}+. HRMS (EI,
m/z): {C11H8PO3Mn}+ calcd 273.95917, found 273.95932.
Ch a r a cter iza tion of 34. 31P{1H} NMR (CH2Cl2): δ 81.1.
IR: νCO 2088 (s); 2048 (m), 2012 (s); 1980 (br, s), 1932 (m);
Ack n ow led gm en t. Dr. Larry Calhoun (UNB) is
thanked for assistance with the NMR experiments and
Mr. Gilles Vautour (UNB) for mass spectrometry. We
are grateful to the Natural Sciences and Engineering
Research Council of Canada for financial support of this
work.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal-
lographic data, atom coordinates, bond distances, bond angles,
and isotropic and anisotropic displacement parameters. 31P,
1H, and 13C NMR spectra. This material is available free of
charge via the Internet at http://pubs.acs.org.
OM040022K
(45) SAINT 6.02; Bruker AXS, Inc.: Madison, WI, 1997-1999.
(46) Sheldrick, G. SADABS; Bruker AXS, Inc.: Madison, WI, 1999.
(47) Sheldrick, G. SHELXTL 5.1; Bruker AXS, Inc.: Madison, WI,
1997.
1930 (m) cm-1. MS (EI, m/z (%), assignment): 574 (1) {C23H13
-