Steering of configuration by (2-phosphanyl)phenolato ligands in trimethylphosphane iron complexes

Article abstract of DOI:10.1002/zaac.200500021

(Diphenylphosphanyl)phenols C₆H₃(1-OH)(2-PPh ₂)(4-R¹)(6-R²), abbreviated as (P∧OH), oxidatively add to Fe(PMe₃)₄ affording hydridoiron(II) compounds fac-FeH(P∧O)(PMe₃)₃ (1: R¹ = R² = H; 2: R¹ = Me, R² = H; 3: R¹ = OMe, R² = H; 4: R¹ = Me, R² = CMe₃; 5: R¹ = R² = CMe₃) with high stereoselectivity. (2-diphenylphosphanyl)thiophenol (P∧SH) reacts accordingly forming fac-FeH(P∧S)(PMe₃)₃ (9). Complete assignment of ¹H, ¹³C, and ³¹P signals is achieved by 2D heteronuclear shift correlations. 4,6-Di-tert-butyl-(2-diphenylphosphanyl)phenol reacts with FeI(Me)-(PMe₃)₄ to form FeI(P∧O)(PMe ₃)₂ (6). 4, 5 and 9 under 1 bar of CO are converted to monocarbonyl derivatives FeH(P∧X)(CO)-(PMe₃)₂ (7, 8: X = O; 10: X = S) which in solution form mixtures of two isomers A and B. 4 and 5 react with their parent phosphanylphenols, respectively, to give diamagnetic complexes Fe(P∧O)₂-(PMe₃) (11, 12) which dissociate trimethylphosphane to give paramagnetic compounds Fe(P∧O)₂. The same phosphanylphenols react with FeCl₃ to afford racemic mixtures of complexes Fe(P∧O)₃ (13, 14). Structural data were also obtained from single crystals of compounds 1, 5, and 11.

Full text of DOI:10.1002/zaac.200500021

Steering of Configuration by (2-Phosphanyl)phenolato Ligands in
Trimethylphosphane Iron Complexes
Hans-Friedrich Klein*, Markus Frey, and Shizhen Mao
Darmstadt, Institut für Anorganische Chemie der Technischen Universität Darmstadt
Received December 3rd, 2004.
Abstract. (Diphenylphosphanyl)phenols C6H3(1-OH)(2-PPh2)(4-
R1)(6-R2), abbreviated as (P∧OH), oxidatively add to Fe(PMe3)4
affording hydridoiron(II) compounds fac-FeH(P∧O)(PMe3)3 (1:
R1ϭR2 ϭH; 2: R1ϭMe, R2ϭH; 3: R1ϭOMe, R2ϭH; 4: R1ϭMe,
R2ϭCMe3; 5: R1ϭR2ϭCMe3) with high stereoselectivity. (2-diphe-
nylphosphanyl)thiophenol (P∧SH) reacts accordingly forming fac-
FeH(P∧S)(PMe3)3 (9). Complete assignment of 1H, 13C, and 31P
signals is achieved by 2D heteronuclear shift correlations. 4,6-Di-
tert-butyl-(2-diphenylphosphanyl)phenol reacts with FeI(Me)-
(PMe3)4 to form FeI(P∧O)(PMe3)2 (6). 4, 5 and 9 under 1 bar of
CO are converted to monocarbonyl derivatives FeH(P∧X)(CO)-
(PMe3)2 (7, 8: X ϭ O; 10: X ϭ S) which in solution form mixtures
of two isomers A and B. 4 and 5 react with their parent phospha-
nylphenols, respectively, to give diamagnetic complexes Fe(P∧O)2-
(PMe3) (11, 12) which dissociate trimethylphosphane to give para-
magnetic compounds Fe(P∧O)2. The same phosphanylphenols
react with FeCl3 to afford racemic mixtures of complexes Fe(P∧O)3
(13, 14). Structural data were also obtained from single crystals of
compounds 1, 5, and 11.
Keywords: Iron; Hydrides; Phosphorus ligands; Spin Systems (1H,
13C, 31P)
Introduction
(2-Diphenylphosphanyl)phenols shift this equilibrium by
replacing one of the trimethylphosphane ligands [Equation
(1)] and smoothly afford the novel hydride compounds 1Ϫ5.
Octahedral coordination of phosphane and hydride ligands
by iron(II) atoms in a low-spin state requires sterically non-
demanding donor entities. With trimethylphosphanes in-
terligand repulsion becomes severe at angles PϪFeϪPЈ be-
tween 100 and 90°. Relaxation of crowding can occur either
through bending of the donor atoms towards the hydride
position or in a fluxional state as in FeH2(PMe3)4 where
both H ligands traverse the edges of a tetrahedral FeP4
frame [1].
Coordination of a soft/hard chelating 2-phosphanylphen-
olato ligand under these conditions will help to clarify some
important ligand properties with respect to homogeneous
catalysis of nickel and palladium compounds [2] and the
chelate systems of iron [3].
Firstly, spectroscopy can shed light on the different trans-
influences through the hexa-coordinate metal atom in three
directions. Secondly, structural information will give an idea
of ligand bulkiness and access of substrate molecules. A
third important point would be experimental evidence on
the question of inertness or propensity towards reactions
with the hydride function under elimination of hydrocarbon
or H2.
The pattern of substitution provided in the (2-phosphanyl)-
phenol controls the solubilities of the red crystalline com-
plexes which are obtained from THF/diethyl ether (1,2,4),
pentane/diethylether (3) or pentane solutions (5), in good
to acceptable yields.
Conspicuous
infrared
bands
in
the
region
Results and Discussion
The zerovalent metal center in Fe(PMe3)4 is known to acti-
vate and reversibly add one of its ligand-CH functions [4].
1815Ϫ1875 cmϪ1 where a ν(FeϪH) absorption is expected
and single high-field proton resonances between Ϫ7.5 and
Ϫ9 ppm, each with a pattern arising from coupling to four
different 31P nuclei (see below), are consistent with the pres-
ence of only one isomer in the samples of 1 Ϫ 5.
* Prof. Dr. H.-F. Klein
Eduard-Zintl-Institut für Anorganische und Physikalische Chemie
der TU Darmstadt
Petersenstrasse 18
D-64287 Darmstadt
Tel. (ϩ49) 6151-16-2173
The molecular structures of 1 and 5 (Fig. 1 and 2) both
contain a frame of atoms FeP4O in which two large bond
angles, O1ϪFeϪP3 ϭ 172.6(2)° and P1ϪFeϪP2 ϭ 150.8(1)°
in 1 as well as O1ϪFeϪP3 ϭ 170.7(2)° and P1ϪFeϪP4 ϭ
152.6(2)° in 5, define the site where the hydride function is
Fax: (ϩ49) 6151-16-4173
1516
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
DOI: 10.1002/zaac.200500021
Z. Anorg. Allg. Chem. 2005, 631, 1516Ϫ1523

Steering of Configuration by (2-Phosphanyl)phenolato Ligands
be subject to the strong trans influence of a hydride ligand.
The shortest FeϪP bond is found opposite to the phenolato
donor which is part of the chelate ring (bite angles OϪFeϪP1
are 83.7(2)° in 1 and 83.2(2)° in 5). Thus the three different
FeϪP bond lengths involving the trimethylphosphanes in 1
and likewise in 5 indicate the different vectors of trans influ-
ences in perpendicular directions. The configuration adopted
by both molecules in the crystal is facial with angles
PϪFeϪPЈ ranging from 89 to 101°.
NMR Spectra
In [D8]THF solution all hexacoordinate hydridoiron com-
pounds gave well-resolved NMR spectra (Table 1) and were
either observed as single isomers 1 Ϫ 5 or in the case of
monocarbonyl derivatives as mixtures of two isomers 7A/
7B and 8A/8B. Conspicuous highϪfield proton resonances
show a typical pattern arising from coupling to four or
three anisochronic 31P nuclei, respectively. Replacing the
oxygen by a thio donor causes a high-field shift of that res-
onance in 9 by about 4 ppm. Using double-resonance tech-
niques1) small positive coupling constants were assigned to
Figure 1 Molecular structure of 1 (ORTEP plot without hydrogen
atoms)
˚
Selected bond lengths/A and angles/°: FeϪO1 204.5(6), FeϪP1 221.0(3),
FeϪP2 221.6(3), FeϪP3 217.6(3), FeϪP4 224.6(2), O1ϪC6 131.7(11),
C1ϪC6 140.9(13), P1ϪC1 181.7(9), P1ϪC7 185.0(9); O1ϪFeϪP1 83.7(2),
O1ϪFeϪP2 77.3(2), O1ϪFeϪP3 172.6(2), O1ϪFeϪP4 89.5(2), P1ϪFeϪP2
150.83(10), P1ϪFeϪP3 89.0(1), P1ϪFeϪP4 162.64(9), P2ϪFeϪP3
97.44(11), P2ϪFeϪP4 99.21(11), P3ϪFeϪP4 96.58(10), C1ϪP1ϪFe
100.6(3), C6ϪO1ϪFe 118.9(5), C7ϪP1ϪFe 122.6(3), P1ϪC1ϪC6 112.3(6),
O1ϪC6ϪC1 121.3(8), C7ϪP1ϪC1 101.2(4).
2JP,H while the larger negative values represent 2JP,H
.
trans
cis
2
2
The JP,H as well as the JP,P values are not sensitive to
electronic effects neither in the aromatic backbone of the
(2-phosphanyl)phenolato ligands nor in changing an O for
an S donor atom but clearly show the expected angular de-
pendence [5].
Complete assignment of 1H, 13C, and 31P signals is based
on two-dimensional heteronuclear shift correlations.1) The
31P NMR data are presented in Table 2, while 13C data and
other spectroscopic details are given in the experimental
section.
Derivatives and Reactions
Carbon monoxide selectively displaces one of the trimeth-
ylphosphanes in 4 or 5 [Equation (2)].
Figure 2 Molecular structure of 5 (ORTEP plot without hydrogen
atoms)
˚
Selected bond lengths/A and angles/°: FeϪO1 208.3(7), FeϪP1 221.5(4),
FeϪP2 225.3(4), FeϪP3 218.6(4), FeϪP4 224.0(4), O1ϪC1 136.4(9), C1ϪC6
139(1), P1ϪC1 179.6(6), P1ϪC21 188.6(6); O1ϪFeϪP1 83.2(2), O1ϪFeϪP2
91.4(2), O1ϪFeϪP3 170.7(2), O1ϪFeϪP4 79.5(2), P1ϪFeϪP2 101.78(13),
P1ϪFeϪP3 89.57(14), P1ϪFeϪP4 152.6(2), P2ϪFeϪP3 97.10(4),
P2ϪFeϪP4 99.76(14), P3ϪFeϪP4 95.4(2), C6ϪP1ϪFe 100.8(2),
C1ϪO1ϪFe 120.5(5), C15ϪP1ϪFe 123.6(3), P1ϪC6ϪC1 117.4(3),
O1ϪC1ϪC6 116.7(4), C15ϪP1ϪC21 102.1(3).
1) We thank Prof. B. Wrackmeyer, University of Bayreuth, Ger-
many, for the more elaborate NMR measurements.
attachted. In the opposite position we find a trimethylphos-
phane ligand at the longest FeϪP distance which appears to
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Table 1 FeϪH proton resonances (500 MHz, THF-D8) of 1 Ϫ 5, 7A, 7B, 8A, 8B, and 9
Compound
No.
δ FeϪH
ppm
2J(PAH)
Hz
2J(PBH)
Hz
2J(PCH)
Hz
2J(PDH)
Hz
R1ϭR2ϭH; XϭO
1
2
3
4
Ϫ8.9, dddd
Ϫ8.9, dddd
Ϫ7.7, dddd
Ϫ8.7, dddd
Ϫ8.7, dddd
Ϫ8.5, ddd
Ϫ7.1, ddd
Ϫ8.5, ddd
Ϫ7.1, ddd
Ϫ12.9, ddd
Ϫ72
Ϫ72
Ϫ72
Ϫ70
Ϫ63
Ϫ67
Ϫ71
Ϫ68
Ϫ71
Ϫ83
Ϫ62
Ϫ62
Ϫ63
Ϫ58
Ϫ55
Ϫ65
Ϫ
Ϫ65
Ϫ
Ϫ58
Ϫ54
Ϫ54
Ϫ54
Ϫ56
Ϫ53
Ϫ
Ϫ53
Ϫ
Ϫ53
Ϫ50
ϩ37
ϩ37
ϩ37
ϩ38
ϩ40
ϩ53
ϩ53
ϩ53
ϩ53
ϩ33
R1ϭMe; R2ϭH; XϭO
R1ϭOMe; R2ϭH; XϭO
R1ϭMe; R2ϭtBu; XϭO
R1ϭR2ϭtBu; XϭO
R1ϭMe; R2ϭtBu; XϭO
R1ϭMe; R2ϭtBu; XϭO
R1ϭR2ϭtBu; XϭO
R1ϭR2ϭtBu; XϭO
R1ϭR2ϭH; XϭS
5
7A
7B
8A
8B
9
Table 2 31P magnetic resonances (202 MHz, THF-D8) of 1 Ϫ 5, 7A, 7B, 8A, and 8Ba)
Compound
No.
δ PA
δ PB
δ PC
δ PD
R1ϭR2ϭH
1
2
3
4
76.6, ddd
75.7, ddd
77.6, ddd
80.1, ddd
80.8, ddd
63.1, t
78.5, dd
63.6, d
78.5, dd
88.0, ddd
37.8, ddd
37.8, ddd
37.7, ddd
36.5, ddd
37.5, ddd
19.6, d
Ϫ
19.4, d
Ϫ
27.6, ddd
24.2, ddd
24.4, ddd
24.2, ddd
24.4, ddd
24.7, ddd
Ϫ
21.2, dd
Ϫ
21.1, dd
13.3, ddd
14.2, ddd
R1ϭMe; R2ϭH
R1ϭOMe; R2ϭH
R1ϭMe; R2ϭtBu
R1ϭR2ϭtBu
14.4, ddd
14.4, ddd
13.5, ddd
13.6, ddd
19.6, d
7.8, dd
19.4, d
5
R1ϭMe; R2ϭtBu
R1ϭMe; R2ϭtBu
R1ϭR2ϭtBu
7A
7B
8A
8B
9
R1ϭR2ϭtBu
7.8, dd
5.3, ddd
R1ϭR2ϭH; XϭS
Compound
No.
2J(PAPC)
Hz
2J(PAPB)
Hz
2J(PAPD)
Hz
2J(PBPC)
Hz
2J(PBPD)
Hz
2J(PCPD)
Hz
R1ϭR2ϭH
1
2
3
4
ϩ100
ϩ102
ϩ102
ϩ99
ϩ97
Ϫ
ϩ135
Ϫ
ϩ133
ϩ95
Ϫ37
Ϫ36
Ϫ36
Ϫ42
Ϫ41
Ϫ26
Ϫ
Ϫ25
Ϫ
Ϫ42
Ϫ22
Ϫ22
Ϫ22
Ϫ23
Ϫ24
Ϫ26
Ϫ28
Ϫ29
Ϫ26
Ϫ25
Ϫ46
Ϫ45
Ϫ45
Ϫ46
Ϫ46
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ48
Ϫ31
Ϫ30
Ϫ30
Ϫ28
Ϫ27
Ϫ26
Ϫ
Ϫ29
Ϫ
Ϫ34
Ϫ27
Ϫ26
Ϫ26
Ϫ26
Ϫ27
Ϫ
Ϫ23
Ϫ
Ϫ21
Ϫ13
R1ϭMe; R2ϭH
R1ϭOMe; R2ϭH
R1ϭMe; R2ϭtBu
R1ϭR2ϭtBu
5
R1ϭMe; R2ϭtBu
R1ϭMe; R2ϭtBu
R1ϭR2ϭtBu
7A
7B
8A
8B
9
R1ϭR2ϭtBu
R1ϭR2ϭH; XϭS
a) For atom numbering see Table 1.
Infrared spectra of the solids contain single ν(FeϪH) and
ν(CϵO) bands, NMR spectra obtained from THF solu-
tions of 7 or 8 show the presence of stereoisomers A and B
with ratios of 7A/B ϭ 16/84 and 8A/B ϭ 30/70 [Equation
(2)].
A FeCH3 function adjacent to a coordinated (2-dimeth-
ylphosphanyl)ethanol is prone to eliminate methane and
close the metallacycle formally replacing the FeϪH by a
FeϪI function [Equation (3)].
Reaction occurs while allowing an ethereal solution to
warm up, and progress is indicated by a red brown, deep
yellow, and finally yellowish green coloration. Complex 6 is
obtained as green microcrystalline material which is recrys-
tallized from diethyl ether/pentane. THF solutions in NMR
experiments at 25 °C display broad resonances showing a
time-dependent pattern of signals without deposition of
metal. This observation may be due to a small equilibrium
concentration of a diiron species containing either phenoxo
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Steering of Configuration by (2-Phosphanyl)phenolato Ligands
or iodide bridges which convert coordinatively unsaturated
6 to a sterically crowded dimer (18 metal-valence electrons).
In all attempts to prepare this type of complex e.g. by re-
acting compounds 1 Ϫ 4 with moleequivalent amounts of
iodomethane in diethyl ether after 16 h at 20 °C only start-
ing materials were recovered.
Figure 3 Molecular structure of 11 (ORTEP plot without hydrogen
atoms), phenyl rings at P(1) and P(3) have been omitted for clarity
˚
Selected bond lengths/A and angles/°: Fe1ϪO1 1.943(29), Fe1ϪO2
1.959(48), Fe1ϪP1 2.552(39), Fe1ϪP2 2.471(67), Fe1ϪP3 2.529(39), O1ϪC1
1.308(30), O2ϪC24 1.302(25); P1ϪFe1ϪP2 99.37(3), P1ϪFe1ϪP3 156.24(2),
P2ϪFe1ϪP3 104.21(1), O1ϪFe1ϪP1 99.50(3), O1ϪFe1ϪP2 101.48(2),
O1ϪFe1ϪP3 78.76(2), O1ϪFe1ϪO2 157.67(3).
Action of a (2-phosphanyl)phenol on dimethyltetrakis-
(trimethylphosphane)iron does not furnish
a methyl-
(P∧O)iron compound as both FeϪCH3 functions appear to
react with similar rates. Using excess phenolic reagent a
high-yield synthesis affords bis(2-phosphanylphenola-
to)iron compounds 9 and 10 [Equation (4)].
basis of a square pyramid and an axial trimethylphos-
phane ligand.
All attempts at analogous syntheses using (2-phospha-
nyl)phenols without a substituent in the 6-position have so
far met with failure. By reaction of 1 or 2 with excess hydro-
chloric acid under conditions where 11 is generated from
5, the parent phosphanylphenols are formed in a smooth
demetallation process [Equation (6)].
Iron(III) Trischelates
Reacting the disubstituted 2-phosphanylphenols with FeCl3
and an amine [Equation (7)] gives dark violet solutions
which upon extraction with pentane and cooling afford
black crystals of the trischelates 13 and 14 in high yields.
A more convenient synthesis starting with dichlorobis(tri-
methylphosphane)iron in the presence of an amine [Equa-
tion (5)] in most experiments gave lower yields. The hydrido
complex 5 by reaction with either excess HCl or iodome-
thane can be transformed to the bisphenolato species, while
the highest yield was achieved by reacting 5 with its parent
(2-phosphanyl)phenol. The majority of products from these
syntheses consist of green crystals of a pentacoordinate
monotrimethylphosphane complex (11 or 12, respectively)
and a second fraction of black crystals which constitute the
paramagnetic analogue 12ϪP without the trimethylphos-
phane ligand. Crystals of 12ϪP were large enough to be
mechanically separated while the identity of microcrystal-
line 11ϪP among residual 11 is confirmed by elemental
analyses and the absence of characteristic IR bands (PCH3)
in the former.
Solid materials 13 and 14 are air-stable and decompose
above 200 °C. Magnetic susceptibilities obtained from the
racemic mixtures (μeff /μB ϭ 5.85 for 13 and μeff /μB ϭ 5.78
for 14) are close to the spin-only value (μeff /μB ϭ 5.92) and
compatible with a high-spin state of iron (d5) in an octa-
The molecular structure of 11 (Fig. 3) contains a penta-
coordinate iron with transoid chelating O,P ligands at the
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H.-F. Klein, M. Frey, S. Mao
3.22 mmol) in 80 mL of diethyl ether at Ϫ70 °C was combined with
2-(diphenylphosphanyl)(4-methyl)phenol (940 mg, 3.22 mmol) and
upon heating to 20 °C under stirring gave a red brown solution.
After 16 h an orange red solid was formed, and work up proceeded
as with 1 to yield 1180 mg of product (64 %), m.p. 181Ϫ183 °C.
C28H44FeOP4 (572.4): C 57.50 (calc. 58.35), H 7.82 (7.69), P
21.86 (21.49) %.
hedral field of (P,O)3 ligands which for steric reasons is ex-
pected to attain a mer configuration.
Conclusion
(2-Phosphanyl)phenols and (2-phosphanyl)thiophenols oxi-
datively substitute trimethylphosphane in Fe(PMe3)4 to
form fac-(P,O and P,S chelate)tris(trimethylphosphane)iron
hydrides. None of the two possible mer-isomers is observed.
Action of acid giving H2 and positively polarized methyl
groups evolving as methane indicate the hydridic nature of
the FeϪH function. Although dissociation of ligands in
THF solutions at 20 °C is slow on the NMR time scale,
substitution of trimethylphosphane by carbon monoxide
proceeds in a smooth reaction whereas under otherwise
same conditions (1 bar, 20 °C) ethene does not react. The
strongly π-accepting CO ligand alters the balance of trans-
effects in such a way as to allow for equilibria of isomers in
solution retaining the trans-arrangements O(S) ϪFeϪCO,
PϪFeϪH, and PϪFeϪP in the octahedral coordination po-
lyhedra. A 6-tBu substituent renders low-spin and high-
spin bis(P,O-chelate)iron(II) compounds inert towards min-
eral acid and at the same time promotes dissociation of tri-
methylphosphane as a fifth ligand from the axial position
of a square pyramid (low-spin). Tris(P,O-chelate)iron(III)
compounds attain the expected high-spin valence state and
show a high thermal stability.
IR (Nujol): ν(FeϪH) 1837 m cmϪ1
.
1H NMR ([D8]THF): δ ϭ 0.88 (d, 9 H,
2
2JP,H ϭ 6.0 Hz, PCH3), 1.04 (d, 9 H, JP,H ϭ 7.2 Hz, PCH3), 1.48 (d, 9 H,
2JP,H ϭ 7.5 Hz, PCH3), 1.93 (s, 3 H, CCH3), 6.3Ϫ8.5 (m, 13 H) ppm. 13C
1
NMR ([D8]THF): δ ϭ 12.5 (s), 17.9 (d, JP,C ϭ 16.2 Hz, PCH3), 20.5 (d,
1JP,C ϭ 20.4 Hz, PCH3), 29.2 (s, CCH3), 109.6 (d, JP,C ϭ 5.6 Hz, CH), 123.8
(d, JP,C ϭ 49.9 Hz, CH), 126.3 (s, CH), 126.7 (s, CH), 127.4 (s, CH), 129.4
(d, JP,C ϭ 29.0 Hz, CH), 131.8 (d, JP,C ϭ 9.7 Hz, CH), 133.1 (d, JP,C
ϭ
9.4 Hz, CH), 139.0 (d, JP,C ϭ 42.9 Hz, CH), 141.9 (d, JP,C ϭ 16.6 Hz, CCH3),
175.0 (d, JP,C ϭ 23.7 Hz, CO) ppm.
Hydrido[2-(diphenylphosphanyl)(4-methoxy)phenolato-O,P]tris(tri-
methylphosphane)iron(II) (3): A sample of Fe(PMe3)4 (1470 mg,
4.08 mmol) in 80 mL of diethyl ether at Ϫ70 °C was combined with
2-(diphenylphosphanyl)(4-methoxy)phenol (1250 mg, 4.07 mmol)
and upon heating to 20 °C under stirring gave an orange red solu-
tion. After 16 h this was taken to dryness in vacuo, and the residue
was extracted with diethyl ether to yield after cooling to Ϫ28 °C
1300 mg of product (55 %), m.p. 172Ϫ173 °C.
C28H44FeO2P4 (592.3): C 56.96 (calc. 56.77), H 7.40 (7.49), P
20.92 (20.91) %.
IR (Nujol): ν(FeϪH) 1872 m cmϪ1
.
1H NMR ([D8]THF): δ ϭ 0.88 (d, 9 H,
2
2JP,H ϭ 5.9 Hz, PCH3), 1.04 (d, 9 H, JP,H ϭ 7.0 Hz, PCH3), 1.48 (d, 9 H,
2JP,H ϭ 7.5 Hz, PCH3), 3.36 (s, 3 H, OCH3), 6.2Ϫ8.5 (m, 13 H) ppm. 13C
1
NMR ([D8]THF): δ ϭ 12.5 (s), 17.86 (d, JP,C ϭ 16.7 Hz, PCH3), 20.3 (d,
1JP,C ϭ 20.1 Hz, PCH3),54.3 (s, OCH3), 126.3 (s, CH), 126.4 (s, CH), 126.7
(s, CH), 127.5 (S, CH), 131.8 (d, JP,C ϭ 9.7 Hz, CH), 133.0 (d, JP,C ϭ 9.5 Hz,
CH), 146.5 (s, COCH3) ppm.
Hydrido[2-(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenolato-
O,P]tris(trimethylphosphane)iron(II) (4): A sample of Fe(PMe3)4
(660 mg, 1.83 mmol) in 60 mL of diethyl ether at Ϫ70 °C was com-
bined with 2-(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenol
(640 mg, 1.83 mmol) and upon heating to 20 °C under stirring gave
a yellow brown suspension. After 16 h a light brown solid was fil-
tered off and dissolved in diethyl ether/THF (3:2). The brown solu-
tion and the light brown filtrate at Ϫ28 °C gave orange solids which
were identical (IR). Combined yield 760 mg (66 %), m.p.
178Ϫ180 °C.
Experimental Part
General procedures and materials: All air-sensitive and volatile ma-
terials were handled by standard vacuum techniques and kept un-
der argon. Details have been given elsewhere [6]. NMR measure-
ments: Bruker DRX 500 {1H, 13C, 31P}.Chemical shifts are given
relative to Me4Si. Literature methods were used in the preparation
of Fe(PMe3)4 [7], FeMe2(PMe3)4 [4], FeCl2(PMe3)2 [8], Fe(Me)-
I(PMe3)4 [7], (2-diphenylphosphanyl)phenols [9], and (2-diphenyl-
phosphanyl)thiophenol [10]. Other chemicals (Merck-Schuchardt)
were used as purchased.
C32H52FeOP4 (632.5): C 60.12 (calc. 60.77), H 8.13 (8.29), P
19.33 (19.59) %.
Hydrido[2-(diphenylphosphanyl)phenolato-O,P]tris(trimethylphos-
phane)iron(II) (1): A sample of Fe(PMe3)4 (640 mg, 1.78 mmol) in
50 mL of diethyl ether at Ϫ70 °C was combined with 2-(diphenyl-
phosphanyl)phenol (490 mg, 1.78 mmol) and allowed to warm up
under stirring. Upon dissolution of the solid the brown color
changed to orange red. After 16 h an orange red solid was formed
which was filtered off and dissolved in diethyl ether/THF (4:1). The
orange red solution at Ϫ28 °C and the orange filtrate at Ϫ5 °C gave
red crystals which were identical (IR) and were combined to yield
670 mg of product (67 %), dec. > 190 °C.
IR (Nujol): ν(FeϪH) 1817 m cmϪ1
.
1H NMR ([D8]THF): δ ϭ 0. 86 (d, 9 H,
2
2JP,H ϭ 5.0 Hz, PCH3), 1.03 (d, 9 H, JP,H ϭ 6.7 Hz, PCH3), 1.30 (s, 9 H,
CCH3), 1.60 (d, 9 H,2JP,H ϭ 6.8 Hz, PCH3), 1.91 (s, 3 H, CH3), 6.4Ϫ8.6 (m,
12 H) ppm. 13C NMR ([D8]THF): δ ϭ 18.7 (d, 1JP,C ϭ 17.7 Hz, PCH3), 22.1
(tЈ, Η1JP,C
ϩ
3JP,CΗ ϭ 19.6 Hz, PCH3), 28.6 (s, CCH3), 33.5 (s, CCH3), 126.5
(d, JP,C ϭ 21.0 Hz, CP), 127.4 (s, CH), 132.3 (d, JP,C ϭ 9.5 Hz, CH), 133.1
(d, JP,C ϭ 9.8 Hz, CH) ppm.
Hydrido[2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenolato-O,P]-
tris(trimethylphosphane)iron(II) (5):
A sample of Fe(PMe3)4
(360 mg, 1.00 mmol) in 60 mL of diethyl ether at Ϫ70 °C was com-
bined with 2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenol (390
mg, 1.00 mmol) and upon warming up under stirring gave an or-
ange red solution. After 19 h this was taken to dryness in vacuo,
and the residue was extracted with pentane to afford after cooling
to Ϫ28 °C red crystals. Yield 440 mg (65 %), m.p. 182Ϫ183 °C.
C35H58FeOP4 (674.6): C 61.95 (calc. 62.32), H 8.91 (8.67), P
18.25 (18.37) %.
C27H42FeOP4 (562.4): C 57. 26 (calc. 57.67), H 8.30 (7.53), P
21.75 (22.03) %.
IR (Nujol): ν(FeϪH) 1830 m cmϪ1
.
1H NMR ([D8]THF): δ ϭ 0.88 (d, 9 H,
2JP,H ϭ 6.1 Hz, PCH3), 1.04 (d, 9 H, JP,H ϭ 6.7 Hz, PCH3), 1.49 (d, 9 H,
2JP,H ϭ 7.4 Hz, PCH3), 6.0Ϫ8.5 (m, 14 H) ppm. 13C NMR ([D8]THF): δ ϭ
12.5 (s), 17.88 (d, 1JP,C ϭ 16.8 Hz, PCH3), 20.48 (tЈ, Η1JP,C ϩ 3JP,CΗ ϭ 20.4 Hz,
PCH3), 109.6 (d, JP,C ϭ 5.6 Hz, CH), 116.4 (d, JP,C ϭ 7.5 Hz, CH), 126.5
(d, JP,C ϭ 27.3 Hz, CH), 127.6 (d, JP,C ϭ 25.9 Hz, CH), 130.1 (s, CH), 131.8
(d, JP,C ϭ 9.6 Hz, CH), 133.0 (d, JP,C ϭ 9.5 Hz, CH) ppm.
2
IR (Nujol): ν(FeϪH) 1863 m cmϪ1 1H NMR ([D8]THF): δ ϭ 0.87 (s, 9 H,
.
PCH3), 1.03 (s, 9 H, PCH3), 1.06 (s, 9 H, CCH3), 1.32 (s, 9 H, PCH3), 1.62
(s, 9 H, CCH3), 6.7Ϫ8.6 (m, 12 H) ppm. 13C NMR ([D8]THF): δ ϭ 18.8 (d,
Hydrido[2-(diphenylphosphanyl)(4-methyl)phenolato-O,P]tris(tri-
methylphosphane)iron(II) (2): A sample of Fe(PMe3)4 (1160 mg,
1JP,C ϭ 16.5 Hz, PCH3), 22.1 (tЈ, Η1JP,C
ϩ
3JP,CΗ ϭ 21.9 Hz, PCH3), 24.2 (s,
1520
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 1516Ϫ1523

Steering of Configuration by (2-Phosphanyl)phenolato Ligands
CCH3), 28.6 (s, CCH3), 32.5 (s, CCH3), 33.9 (s, CCH3), 123.4 (d, JP,C
ϭ
in 50 mL of diethyl ether was combined at Ϫ70 °C with (2-di-
phenylphosphanyl)thiophenol (760 mg, 2.60 mmol) in 30 mL of di-
ethyl ether. The mixture was warmed to 20 °C and after 16 h had
attained a red color. The volatiles were removed in vacuo and the
solid residue was washed with two 20-mL portions of pentane to
afford a red powder of 9. Yield 1200 mg (80 %), m.p. 166Ϫ168 °C
55.2 Hz, CP), 125.3 (s, CH), 126.6 (d, JP,C ϭ 21.9 Hz, CH),), 132.3 (d, JP,C ϭ
9.3 Hz, CH), 133.2 (d, JP,C ϭ 9.4 Hz, CH), 134.9 (d, JP,C ϭ 7.8 Hz, CCCH3),
139.6 (d, JP,C ϭ 42.7 Hz, CP) 142.20 (d, JP,C ϭ 14.6 Hz, CCCH3), 172.4 (d,
JP,C ϭ 23.3 Hz, CO) ppm.
Iodo[2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenolato-O,P]bis(tri-
methylphosphane)iron(II) (6):
(640 mg, 1.27 mmol) in 60 mL of diethyl ether at Ϫ70 °C was com-
bined with 2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenol
A sample of Fe(Me)I(PMe3)4
(dec. > 180 °C). IR (Nujol): ν(FeϪH) 1845 m cmϪ1
.
C27H42FeP4S (578.4): C 55.65 (calc. 56.06), H 7.08 (calc. 7.32), P
21.85 (21.42), S 5.61 (5.54) %.
(500 mg, 1.27 mmol) and upon warming to 20 °C changed from
red brown to yellowish green. After 19 h the light green mixture
was taken to dryness in vacuo, and the residue was extracted with
diethyl ether to afford after cooling to Ϫ5 °C red crystals. Yield
370 mg (41 %), m.p. 165Ϫ167 °C.
Hydrido(carbonyl)[(2-diphenylphosphanyl)thiophenolato-S,P]bis(tri-
methylphosphane)iron(II) (10): A sample of 9 (500 mg, 0.86 mmol)
in 60 ml of THF was stirred at 20 °C under 1 bar of CO whereby
the color slowly changed from red to yellow. After 16 h the volatiles
were removed in vacuo and the residue was dissolved in 40 mL of
pentane. Slow concentration to a volume of 20 mL within 7 d at
20 °C afforded light brown plates of 10a/10b. Yield 420 mg (92 %),
m.p. 152Ϫ167 °C (dec. > 200 °C).
C32H48FeIOP3 (724.4): C 52.68 (calc. 53.06), H 6.65 (6.68), P
12.87 (12.83) %.
Hydrido(carbonyl)[2-(diphenylphosphanyl)(4-methyl)(6-tert-butyl)-
phenolato-O,P]tris(trimethylphosphane)iron(II) (7): A sample of 4
(500 mg, 0.87 mmol) in 60 mL of diethyl ether was kept under 1 bar
CO for 16 h to form a yellow solution. This was evaporated to
dryness and the residue recrystallised from diethyl ether as yellow
crystals. Yield 420 mg (82 %), m.p. 179Ϫ182 °C.
C25H33FeOP3S (530.4): C 55.88 (calc. 56.62), H 6.53 (6.27), P 17.86
(17.52), S 10.85 (10.53) %.
IR (Nujol): ν(CϵO) 1935 vs, 1897 vs, ν(FeϪH) 1845 m cmϪ1 1H NMR
.
2
2
(500 MHz, [D8]THF): Ϫ10.8 (ddd, 1 H, JP(A),H ϭ 57 Hz, JP(C),H ϭ 47 Hz,
2JP(D),H ϭ 105 Hz, FeϪH), Ϫ9.9 (dt, 1 H, JP(A),H ϭ 68 Hz, JP(E),H
ϭ
ϩ
2
2
42 Hz, FeϪH), 0.87 (d, 9 H, JP,H ϭ 7.3 Hz, PDCH3), 0.93 (tЈ, 9 H, Η2JP,H
2
C30H43FeO2P4 (584.4): C 61.58 (calc. 61.66), H 7.43 (7.42), P 1.04
(15.90) %.
4JP,HΗ ϭ 7.5 Hz, PECH3), 1.59 (dd, 2JP,H ϭ 8.4 Hz, 4JP(A),H ϭ 1 Hz, PCCH3),
6.68 (dddd, 1 H, 3J ϭ 7.3 Hz, 3J ϭ 7.0 Hz, 4J ϭ 2.2 Hz, 4J ϭ 1.5 Hz, C(4)H),
IR (Nujol): ν(CϵO) 1882 vs, ν(FeϪH) 1843 m cmϪ1
.
1H NMR ([D8]THF):
3
3
4
4
6.90 (dddd, 1 H, J54 ϭ 7.3 Hz, J34 ϭ 7.0 Hz, J64 ϭ 1.1 Hz, JP(A)4
ϭ
2
δ ϭ 0.85 (d, 9 H, JP,H ϭ 7.3 Hz, PCH3), 0.92 (s, 9 H, PCH3), 0.93 (s, 9 H,
2.0 Hz, C(4)H), 6.99 (dddd, 1 H, 3J43 ϭ 7.0 Hz, 4J53 ϭ 2.7 Hz, 5J63 ϭ 0.7 Hz,
CCH3), 1.32 (s, 9 H, CCH3), 1.35 (s, 9 H, PCH3), 2.11 (s, 3 H, CH3), 2.29 (s,
3JP(A)3 ϭ 5.3 Hz, C(3)H), 7.09 (dddd, 1 H, 3J65 ϭ 8.0 Hz, 3J45 ϭ 7.3 Hz, 4J ϭ
3 H, CH3), 7.1Ϫ7.5 (m, 12 H) ppm. 13C NMR ([D8]THF): δ ϭ 15.5 (d,
4
2.0 Hz, J35 ϭ 2.0 Hz, C(5)H), 7.26Ϫ7.41 (m, 13 H, m-CH, p-CH, C(5)H),
1
1JP,C ϭ 19.5 Hz, PCH3), 19.0 (s, CH3), 19.2 (s, CH3), 19.9 (d, JP,C
ϭ
7.45 (dddd, 1 H, 3J ϭ 8.0 Hz, 4J ϭ 3.0 Hz, JP,H ϭ 1.1 Hz, 5J ϭ 0.7 Hz,
4
23.0 Hz, PCH3), 28.4, 28.6 (s, CCH3), 33.7, 33.9 (s, CCH3), 112.4 (d, 1JP,C ϭ
44.8 Hz, CP), 126.4, 126.5 (s, CH), 127.2 (d, JP,C ϭ 17.6 Hz, CH), 128.4,
128.8 (s, CH), 130.7 (d, JP,C ϭ 11.2 Hz, CH), 131.0 (d, J JP,C ϭ 10.3 Hz,
CH) 133.5 (d, JP,C ϭ 10.3 Hz, CH), 137.3 (s, CCH3), 139.1 (d, JP,C ϭ 8.7 Hz,
CP), 140.5 (s, CCCH3), 141.0 (s, CCCH3), 175.6 (s, CO), 176.1 (s, CO) ppm.
C(6)H), 7.60 (ddd, 1 H, JP,H ϭ 5.7 Hz, 4J ϭ 1.6 Hz, 4J ϭ 1.4 Hz, C(2)H),
3
3
4
5
4
7.65 (dddd, 1 H, J56 ϭ 8.0 Hz, J46 ϭ 1.1 Hz, J36 ϭ 0.7 Hz, JP(A)6
ϭ
3.0 Hz, C(6)H), 7.81Ϫ7.93 (m, 4 H, o-CH). 13C NMR (125 MHz, [D8]THF)
10a: δ ϭ 19.9 [dtЈ, Η1J(PCC) ϩ 3J(PCC)Η ϭ 29.0 Hz, PCCH3], 120.1 [d,
3J(PCC) ϭ 4.0 Hz, C(6)H], 129.7 (d, 4J(PAC) ϭ 2.0 Hz, C(5)H), 129.3 (d,
4J(PAC) ϭ 2.0 Hz, C(p)H), 131.9 (dt, 3J(PAC) ϭ 13.0 Hz, 5J(PEC) ϭ 2.0 Hz,
Hydrido(carbonyl)[(2-diphenylphosphanyl)(4,6-di-tert-butyl)pheno-
C
(4)H), 130.1 (dt, 2J(PAC) ϭ 13.0 Hz, 4J(PEC) ϭ 1.0 Hz, C(3)H), 128.9 (d,
lato-O,P]bis(trimethylphosphane)iron(II) (8):
A
sample of
5
3J(PAC) ϭ 9.0 Hz, C(m)H), 132.5 (d, 2J(PAC) ϭ 10.0 Hz, C(o)H), 135.3 (d,
1J(PAC) ϭ 55.0 Hz, C(i)H), 142.7 (dt, 2J(PAC) ϭ 31.0 Hz, 3J(PEC) ϭ 6.0 Hz,
(360 mg, 0.53 mmol) in 70 mL of diethyl ether was stirred at 20 °C
under 1 bar CO for 16 h. The yellow solution was taken to dryness
in vacuo, and the residue was extracted with pentane to afford after
cooling to Ϫ5 °C yellow crystals. Yield 290 mg (87 %), m.p.
179Ϫ181 °C.
C
(1)H), 166.6 (d, 1J(PAC) ϭ 47.0 Hz, C(2)H), 221.2 (m, CO); 10b: δ ϭ 18.3
[ddd, 1J(PDC) ϭ 23.0 Hz, 3J(PAC) ϭ 2.0 Hz, PDCH3], 22.2 [dd, 1J(PCC) ϭ
27.0 Hz, 3J(PAC)Η ϭ 3.0 Hz, PCCH3], 129.8 (d, 4J(PAC) ϭ 2.0 Hz, C(5)H),
129.4 (d, 4J(PAC)
ϭ
2.0 Hz,
3J(PCC) ϭ 2.0 Hz, 3J(PDC) ϭ 2.0 Hz, C(4)H), 128.3 (d, 2J(PAC) ϭ 10.0 Hz,
(3)H), 132.7 (d, 2J(PAC) ϭ 10.0 Hz, C(o)H), 140.3 (dd, 1J(PAC) ϭ 55.0 Hz,
C ϭ 12.0 Hz,
(p)H), 130.1 (ddd, 3J(PAC)
C
C33H49FeO2P3 (626.5): C 62.88 (calc. 63.27), H 7.19 (7.88), P 15.3
(14.83).
3J(PCC) ϭ 6.0 Hz, C(i)H), 143.0 (ddd, 2J(PAC) ϭ 22.0 Hz, 3J(PCC) ϭ 7.0 Hz,
3J(PDC) ϭ 1.0 Hz, C(1)H), 163.4 (ddd, 1J(PAC) ϭ 38.0 Hz, 3J(PCC) ϭ
12.0 Hz, 3J(PDC) ϭ 3.0 Hz, C(2)H), 219.5 (m, CO). 31P NMR (202 MHz,
[D8]THF) 10a (66 %): δ ϭ 14.0 [d, 2 P, 2J (PA PE) ϭ 28 Hz], 84.5 [t, 1 P, 2J
(PE PA) ϭ 28 Hz]; 10b (33 %): δ ϭ 3.6 [dd, 1 P, 2J (PA PD) ϭ 25 Hz, 2J (PC
PD) ϭ 16.6 Hz], 18.7 [dd, 1 P, 2J (PA PC) ϭ 117 Hz, 2J (PD PC) ϭ 16.6 Hz],
93.1 [dd, 1 P, 2J (PC PA) ϭ 117 Hz, 2J (PD PA) ϭ 25 Hz].
IR (Nujol): ν(CϵO) 1903 vs, ν(FeϪH) 1883 m cmϪ1 1H NMR ([D8]THF):
.
0.85 (s, 9 H, PCH3), 1.19 (s, 9H, CCH3), 1.34 (s, 9 H, CCH3), 1.63 (s, 9 H,
1
PCH3), 7.3Ϫ7.7 (m, 12 H) ppm. 13C NMR ([D8]THF): δ ϭ 20.9 (d, JP,C
ϭ
3
16.6 Hz, PDCH3), 24.2 (d, 1JP,C ϭ 19.5 Hz, JP,C ϭ 3.6 Hz, PCCH3), 26.2 (d,
1JP,C ϭ 20.0 Hz, PBCH3), 28.4 (s, CCH3), 30.4 (s, CCH3), 32. 7 (s, CCH3),
34.0 (s, CCH3), 123.8 (s, CH), 126.4 (d, JP,C ϭ 9.8 Hz, CH), 127.0 (d, JP,C ϭ
8.1 Hz, CH),), 131.0 (d, JP,C ϭ 10.2 Hz, CH), 133.6 (d, JP,C ϭ 10.1 Hz,
CCCH3) ppm.
Bis[2-(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenolato-O,P]-
(trimethylphosphane)iron(II) (11):
Method a: A sample of 4 (580 mg, 0.92 mmol) in 60 mL of diethyl
ether at Ϫ70 °C was combined with aqueous HCl (2.76 ml, 1 M)
and allowed to warm under stirring. After 16 h at 20 °C a white
solid had separated from a light green solution. The volatiles were
removed in vacuo, and the residue was extracted with pentane to
afford after cooling to Ϫ28 °C green crystals. Yield 330 mg (43 %).
Method b: A sample of 4 (630 mg, 1.00 mmol) and of 2-
(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenol (350 mg 1.00
mmol) in 70 mL of THF were allowed to react at 20 °C for 48 h.
The resulting dark green solution was evaporated to dryness and
the residue extracted with pentane. Upon slow cooling to Ϫ5 °C
lustruous green crystals were obtained. Yield 460 mg (56 %).
1
Numbering Scheme for H, 13C and 31P NMR data of complexes
9 and 10
Hydrido[2-(diphenylphosphanyl)thiophenolato-S,P]tris(trimethyl-
phosphane)iron(II) (9): A sample of Fe(PMe3)4 (930 mg, 2.60 mmol)
Method c: A sample of FeMe2(PMe3)4 (590 mg, 1.51 mmol) and 2-
(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenol (1050 mg, 3.01
Z. Anorg. Allg. Chem. 2005, 631, 1516Ϫ1523
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1521

H.-F. Klein, M. Frey, S. Mao
Table 3 Crystal data for compounds 1, 5 and 112).
1
5
11
Empirical formula
Molecular mass
Crystal size /mm
Crystal system
Space group
C27H42FeOP4
562.4
C35H58FeOP4
674.6
0.33 ϫ 0.43 ϫ 0.42
monoclinic
P21/c
11.980(7)
20.962(11)
16.058(9)
90
98.31(5)
90
3991(4)
4
1.123
0.513
293(2)
3.2Յ 2Θ Յ45
Ϫ14 Յ h Յ 14
0 Յ k Յ 24
0 Յ l Յ 19
5202
4963
328
1.096
0.0909
0.3671
C49H57FeO2P3
826.7
0.23 ϫ 0.11 ϫ 0.34
triclinic
0.23 ϫ 0.34 ϫ 0.37
orthorhombic
P212121
10. 740(2)
16.315(2)
17.007(3)
90
90
90
2980.3(8)
4
1.184
0.313
293(2)
3.4Յ 2Θ Յ60
0 Յ h Յ 15
0 Յ k Յ 22
0 Յ l Յ 23
4802
4796
299
1.080
0.0685
PϪ1
˚
a /A
11.037(6)
12.674 (5)
17.571(10)
83.74(4)
77.06(4)
83.66(4)
2372.2(2)
2
1.158
0.409
293(2)
5.2Յ 2Θ Յ50
Ϫ12 Յ h Յ 13
Ϫ14 Յ k Յ 15
0 Յ l Յ 20
8302
8263
497
˚
b /A
˚
c /A
Ͱ /°
β /°
γ /°
3
˚
V /A
Z
Dcalcd. /(g/cm3)
μ(MoKa) /mmϪ1
Temperature /K
Data coll. range /°
h
k
l
No. reflect. measured
No. unique data
Parameters
GoF on F2
R1 (IՆ2σ(I))
wR2 (all data)
1.733
0.1414
0.4912
0.2360
2) Crystallographic data for the structures have been deposited with the Cambridge Crystallographic Data Centre CCDC-260310 (1), -260311 (5), and -260312
(11) as supplementary material for this paper. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: int. codeϩ (1223)336-033, e-mail for inquiry: fileserve@ccdc.cam.ac.uk; e-mail for deposition: deposit@ccdc.cam.ac.uk).
mmol) in 80 mL of diethyl ether at Ϫ70 °C formed a brown solu-
tion which upon warming to 20 °C turned dark green under evol-
ution of gas. After 12 h workup as in method a afforded green
crystals of 9. Yield 830 mg (82 %), m.p. 210Ϫ212 °C.
C49H57FeO2P3 (826.7): C 70.80 (calc. 71.19), H 6.68 (calc. 6.95), P
11.48 (calc. 11.24) %.
Method (d): Samples of FeCl2(PMe3)2 (790 mg, 2.83 mmol), 2-
(diphenylphosphanyl)(4,6-di-tert-butyl)phenol (2210 mg, 5.66
mmol), and diisopropylamine (570 mg, 5.66 mmol) in 60 mL of
THF at Ϫ70 °C while warming up gave a green mixture which was
stirred for 19 h to become dark green. Evaporation to dryness and
extraction with pentane as in (a) afforded 12 as green crystals
(950 mg, 37 %) followed by 12؊P as a second fraction of black
crystals (520 mg, 22 %).
Bis[2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenolato-O,P](tri-
methylphosphane)iron(II) (12) and bis[2-(diphenylphosphanyl)(4,6-di-
tert-butyl)phenolato-O,P]iron(II) (12؊P):
Method (e): A sample of 5 (940 mg, 1.40 mmol) and iodomethane
(990 mg, 7.0 mmol) in 60 mL of diethyl ether were allowed to react
for 72 h. A white solid had separated from a dark violet solution.
The volatiles were removed in vacuo, and the resulting solid was
extracted with pentane to afford black crystals of 12؊P as single
fraction (760 mg, 65 %).
12 [as obtained by method (b)]: m.p 220Ϫ222 °C.
C55H69FeO2P3 (910.9): C 72.35 (calc. 72.52), H 7.75 (7.64), P
10.16 (10.20) %.
Method (a): A sample of 5 (850 mg, 1.27 mmol) in 60 mL of diethyl
ether at Ϫ70 °C were combined with aqueous HCl (6.33 mL, 1 M),
and after a few seconds the light green mixture was allowed to
warm under stirring. After 16 h at 20 °C a dark green solution was
obtained. The volatiles were removed in vacuo, and the residue was
extracted with pentane to afford after cooling to Ϫ5 °C green crys-
tals of 12. Yield 380 mg (33 %). The mother liquor was concen-
trated, and at Ϫ78 ° black crystals of 12؊P were frozen out
(53 mg, 5 %).
10؊P [as obtained by method (e)]: m.p 318Ϫ320 °C.
C52H60FeO2P2 (834.8): C 75.39 (74.81), H 7.56 (calc. 7.24), P 7.13
(7.42) %.
Method (b):
(diphenylphosphanyl)(4,6-di-tert-butyl)phenol
A
sample of
5
(670 mg, 1.00 mmol) and 2-
(390 mg, 1.00
Tris[2-(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenolato-O,P]-
iron(III) (13): Anhydrous FeCl3 (203 mg, 1.25 mmol), 2-
mmol) in 60 mL of diethyl ether were stirred for 24 h. The green
mixture was evaporated to dryness and the residue extracted with
pentane. Upon slow cooling to Ϫ5 °C green crystals of 12 were
obtained. Yield 610 mg (67 %).
(diphenylphosphanyl)(4-methyl)(6-tert-butyl)phenol
(1310 mg,
3.75 mmol), and diisopropylamine (380 mg, 3.73 mmol) in 70 mL
of THF after 16 h produced a dark blue mixture. This was taken
to dryness in vacuo, and the resulting solid was extracted with pen-
tane. At Ϫ5 °C the blue solution afforded black lustrous crystals
of 13. Yield 1200 mg (88 %), m.p. 201Ϫ203 °C. MS (FD): m/z ϭ
1098 (Mϩ, 100 %), 751 (MϪligand, 36 %), 347 (ligandϪH, 26 %).
C69H72FeO3P3 (1098.1): C 75.85 (calc. 75.47), H 6.83 (6.61), P
7.10 (8.46) %.
Method (c): A sample of FeMe2(PMe3)4 (500 mg, 1.28 mmol) and
2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenol (1000 mg 2.56
mmol) in 70 mL of diethyl ether at Ϫ70 °C formed a brown solu-
tion which upon warming to 20 °C turned dark green under evol-
ution of gas. After 16 h workup as in (a) afforded 12 as green crys-
tals (290 mg, 82 %) and 12؊P as black crystals (180 mg, 17 %).
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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Z. Anorg. Allg. Chem. 2005, 631, 1516Ϫ1523

Steering of Configuration by (2-Phosphanyl)phenolato Ligands
Tris[2-(diphenylphosphanyl)(4,6-di-tert-butyl)phenolato-O,P]iron-
(III) (14): Anhydrous FeCl3 (230 mg, 1.43 mmol), 2-
(diphenylphosphanyl)(4,6-di-tert-butyl)phenol (1680 mg, 4.30
mmol), and diisopropylamine (440 mg, 4.30 mmol) in 60 mL of
THF after 16 h gave a dark violet mixture. This was taken to dry-
ness in vacuo, and the resulting solid was extracted with pentane.
At Ϫ5 °C the blue solution afforded black crystals of 14. Yield
1350 mg (78 %), m.p. 233Ϫ235 °C. MS (FD): m/z ϭ 1224 (Mϩ,
100 %), 834 (MϪligand, Ϫ2H, 5 %), 347 (ligandϪH, 26 %).
C78H90FeO3P3 (1224.3): calcd. C 76.52, H 7.41, P 7.59; found C
76.06, H 8.07, P 7.12 %.
References
[1] P. Meakin, E. L. Muetterties, J. P. Jesson, J. Am. Chem. Soc.
1973, 95, 75Ϫ88.
[2] a) W. Keim, New J. Chem. 1987, 11, 531Ϫ534. b) W. Keim, J.
Mol. Catal. 1989, 52, 19Ϫ25.
[3] a) G. J. P. Britovsek, V. C. Gibson, B. S. Kimberley, P. J. Mad-
dox, S. J. McTavish, G. A. Solan, A. J. P. White, D. J. Williams,
J. Chem. Soc., Chem. Commun. 1998, 849Ϫ851. b) B. L. Small,
M. Brookhart, A. M. A. Bennett, J. Am. Chem. Soc. 1998,
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[4] H. H. Karsch, H.-F. Klein, H. Schmidbaur, Chem. Ber. 1977,
110, 2200Ϫ2212.
[5] Multinuclear NMR, J. Mason (ed.), Plenum Press, New York,
London 1987, p. 395.
[6] H.-F. Klein, A. Bickelhaupt, T. Jung, G. Cordier, Organomet-
allics 1994, 13, 2557Ϫ2559.
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Crystal Structure Analyses:
Crystal data are presented in Table 3. Data collection: Complexes
1, 5, and 11: A red specimen (1 and 5) or a green specimen (11),
was glued onto a glass rod and mounted on a Siemens P4 dif-
fractometer. Using graphite-monochromated MoϪKα radiation
lattice parameters were obtained from 25 centered reflections.
Intensities were measured (ω scan) and absorption corrections were
applied. The structures were solved using statistical and Fourier
methods. All non-hydrogen atoms were held in idealised fixed posi-
tions.
Z. Anorg. Allg. Chem. 2005, 631, 1516Ϫ1523
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