Steric control of cyclometallation reactions in Schiff-base complexes of cobalt(I) containing an anchoring diphenylphosphanyl group

Article abstract of DOI:10.1002/1099-0682(200212)2002:12<3305::AID-EJIC3305>3.0.CO;2-A

2-(Diphenylphosphanyl)alkyliminobenzaldehydes (2-Ph₂PC₆H₄CHNR) react with [CoCH₃(PMe₃)₄] forming five-membered metallacycles in complexes [(2-Ph₂PC₆H₄CNR-C,P)Co (PMe₃)₃] [1: R = C₂H₅, 2: R = CH(CH₃)₂, 3: R = cyclo-C₆H11] while the ortho-metallation pathway is selectively followed in the formation of [{2-Ph₂PC₆H₃(CHNR)-C¹,P}Co (PMe₃)₃] [4: R = C(CH₃)₃]. The presence of a four-membered cobaltocycle in the molecular structure of 4 was confirmed by X-ray analysis. Carbonylation of 2 and 3 gives the monocarbonyl derivatives [(2-Ph₂PC₆H₄CNR-C,P)Co(C-O) (PMe₃)₂] [5: R = CH(CH₃)₂, 6: R = cyclo-C₆H₁₁] while 4 undergoes ring expansion by insertion forming [{2-Ph₂PC₆H₃(CHNR)CO-C,P}Co(CO) (PMe₃)₂] [7: R = C(CH₃)₃], Monosubstitution occurs under 1 bar of ethene giving the π-ethene complexes [(2-Ph₂PC₆H₄CNR-C, P)Co(C₂H₄)(PMe₃)₂] [8: R = CH(CH₃)₂, 9: R = cyclo-C₆H₁₁] and [{2-Ph₂PC₆H₃(CHNR)-C¹,P}Co (C₂H₄)(PMe₃)₂] [10: R = C(CH₃)₃]. The molecular structure of 9 shows an equatorial π-ethene ligand Iodomethane oxidizes 2 and 3 to afford the cobalt(II) complexes [(2-Ph₂PC₆H₄CNR-C, P)CoI(PMe₃)₂] [11: R = CH(CH₃)₂, 12: R = cyclo-C₆H₁₁] and oxidatively adds to 4 to give mer-trans-[{2-Ph₂PC₆H₃(CHNR)-C¹, P}CoI(CH₃)(PMe₃)₂] [13: R = C(CH₃)₃]. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002).

Full text of DOI:10.1002/1099-0682(200212)2002:12<3305::AID-EJIC3305>3.0.CO;2-A

FULL PAPER
Steric Control of Cyclometallation Reactions in Schiff-Base Complexes of
Cobalt( ) Containing an Anchoring Diphenylphosphanyl Group
I
Hans-Friedrich Klein,*[a] Robert Beck,[a] Ulrich Flörke,[b] and Hans-Jürgen Haupt[b]
Keywords: Cyclometallation / Cobalt / P ligands / Schiff bases / Regioselectivity
2-(Diphenylphosphanyl)alkyliminobenzaldehydes (2-
Ph2PC6H4CHNR) react with [CoCH3(PMe3)4] forming five-
membered metallacycles in complexes [(2-Ph2PC6H4CNR-
C,P)Co(PMe3)3] [1: R = C2H5, 2: R = CH(CH3)2, 3: R = cyclo-
C6H11] while the ortho-metallation pathway is selectively fol-
lowed in the formation of [{2-Ph2PC6H3(CHNR)-
C1,P}Co(PMe3)3] [4: R = C(CH3)3]. The presence of a four-
membered cobaltocycle in the molecular structure of 4 was
confirmed by X-ray analysis. Carbonylation of 2 and 3 gives
Monosubstitution occurs under 1 bar of ethene giving the π-
ethene complexes [(2-Ph2PC6H4CNR-C,P)Co(C2H4)(PMe3)2]
[8:
R
=
CH(CH3)2, 9:
R
=
cyclo-C6H11
]
and [{2-
Ph2PC6H3(CHNR)-C1,P}Co(C2H4)(PMe3)2] [10: R = C(CH3)3].
The molecular structure of 9 shows an equatorial π-ethene
ligand. Iodomethane oxidizes 2 and 3 to afford the cobalt(II
)
complexes [(2-Ph2PC6H4CNR-C,P)CoI(PMe3)2] [11:
R
=
CH(CH3)2, 12: R = cyclo-C6H11] and oxidatively adds to 4 to
give mer-trans-[{2-Ph2PC6H3(CHNR)-C1,P}CoI(CH3)(PMe3)2]
the monocarbonyl derivatives [(2-Ph2PC6H4CNR-C,P)Co(C- [13: R = C(CH3)3].
O)(PMe3)2] [5: R = CH(CH3)2, 6: R = cyclo-C6H11] while 4
undergoes ring expansion by insertion forming [{2-
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
Ph2PC6H3(CHNR)CO-C,P}Co(CO)(PMe3)2] [7: R = C(CH3)3].
2002)
Introduction
valence electrons and steric limitations, show an active par-
ticipation of the neighbouring N-donor whenever needed.
Therefore, in Schiff-base complexes of transition metal
ions six-membered rings are the dominant structural fea-
tures, and complexes of the chelating ligands B are no excep-
tion, as shown by the few reported examples of complexes
of these ligands with cobalt,[3] molybdenum,[4] rhodium,[5]
and iridium.[6] Preferred coordination of the N-donor would
appear to prevent an attack of the metal at the CϪH bond
which would explain the scarcity of iminoacyl metal com-
plexes arising from CϪH activation.[7] However, in cyclo-
metallation reactions with [CoMe(PMe3)4] there is evidence
for steric control being dominant.[8] Consequently we have
studied the effect of a bulky N-substituent in our investi-
gation of the prechelate species B.
Methylnickel complexes have been shown to activate the
CHO function of 2-diphenylphosphanylbenzaldehyde for-
ming acylnickel compounds.[1]
We have recently described cobalt() complexes con-
taining soft/hard P,N-chelating ligands,[2] where the intro-
duction of an imino ligand function increases the softness
of the N-donor. The isoelectronic relationship between 2-
diphenylphosphanyl benzaldehyde A and its Schiff base de-
rivatives B raises the possibility of a cyclometallation route
to iminoacyl metal complexes. The coordination modes of
iminoacyl complexes, which depend on the number of metal
[a]
Eduard-Zintl-Institut für Anorganische und Physikalische
Chemie
der
Technischen
Universität
Darmstadt,
Petersenstrasse 18, 64285 Darmstadt, Germany
[b]
Anorganische und Analytische Chemie der Universität
Paderborn,
Warburger Straße, 33098 Paderborn, Germany
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312  2002 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/02/1212Ϫ3305 $ 20.00ϩ.50/0 3305

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
Results and Discussion
Metallation Reactions
Angular distortions of the tbp geometry can be expected
in a configuration [(E)-alkyliminoacyl] where the ethyl sub-
stituent is sterically accommodated within the ligand
sphere. Therefore the larger substituents in 2 and 3 are ex-
clusively arranged in the opposite Z-configuration.
An iminoacyl side-chain containing an N-donor function
and an activated CϪH bond was attached to one of the
six ortho-positions of triphenylphosphane to give the Schiff-
base compounds 2-(diphenylphosphanyl)alkyliminobenzal-
dehyde. Reaction with [CoMe(PMe3)4] proceeded at Ϫ70 °C
in THF [Equation (1)] and afforded the C-metallated com-
plexes 1Ϫ3.
At first glance 2-diphenylphosphanyl-tert-butylbenzimide
appeared to react similarly as evolution of a gas was ob-
served at Ϫ70 °C. The reaction mixture became a slightly
deeper red colour than 1Ϫ3, and eventually dark red rhom-
bic crystals of 4 were obtained from pentane. However,
upon metallation there is almost no shift in the infrared
1
absorption of the CϭN band (1626 cmϪ1), and in the H
NMR spectrum a singlet resonance (δ ϭ 7.95 ppm) clearly
represents an aldimine proton. The 31P NMR spectrum
shows a pattern of resonances well-known from ortho-
metallated complexes,[8] strongly suggesting a regioselective
cyclometallation reaction [Equation (2)].
(1)
Black quadrangular crystals of 1 and 2 were obtained
from pentane solution while 3 formed dark brown scales.
Decomposition was noticed above 109Ϫ113 °C under ar-
gon. The ν(CϭN) absorptions in the IR spectra are shifted
bathochromically (by about 100 cmϪ1) with respect to those
of the free ligands upon metallation. The 31P NMR spectra
of 1Ϫ3 show little variation in the dominant signals. A large
low-field shift of the PPh2 resonances is compatible only
with five-membered cobaltocycles, and two doublets of
doublets for one axial and two equatorial P-donor atoms
(2)
The presence of a four-membered cobaltocycle in 4 was
with almost identical JP,P values indicate a tbp-coordinated confirmed by elucidation of the molecular structure (Fig-
cobalt in 1Ϫ3. Only in the spectrum of 1 (Figure 1) are all ure 2).
the resonances accompanied by those of an isomer (12%)
with quite different coupling constants.
The cobalt atom occupies the central position of a tri-
gonal bipyramid with an axial C1 atom and a PMe3 group
Figure 1. 31P NMR spectrum of 1 (81 MHz, [D8]THF, 203 K)
3306
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312

Schiff-Base Complexes of Cobalt(I)
FULL PAPER
Figure 2. Molecular structure of 4, only one position of disordered tBu and PMe3 groups shown (ORTEP plot with hydrogen atoms
˚
omitted); selected bond lengths [A] and angles [°]: CoϪC1 1.977(4), CoϪP1 2.2075(12), CoϪP2 2.1997(15), CoϪP3 2.1836(14), CoϪP4
2.1821(15), P1ϪC6 1.802(4), C1ϪC6 1.403(5); C1ϪCoϪP1 71.09(12), C1ϪCoϪP2 167.82(12), C1ϪCoϪP3 87.92(12), C1ϪCoϪP4
90.78(12), P1ϪCoϪP2 97.11(5), P1ϪCoϪP3 124.02(5), P1ϪCoϪP4 113.76(5), P2ϪCoϪP3 96.66(6), P2ϪCoϪP4 96.96(6), P3ϪCoϪP4
117.93(6)
(P2). A planar [C,P] metallacycle (sum of internal angles ϭ
The iminoacyl(carbonyl)cobalt complexes 5 and 6 are
360°) spans the axial and equatorial positions with a nar- yellow solids that can be handled in air for several hours
row bite-angle [C1ϪCoϪP1 ϭ 71.09(12)°]. Except for one and under argon are thermally stable up to 165 °C. They
of the equatorial PMe3 groups (P4), which shows rotational are insoluble in pentane or diethyl ether and show moderate
disorder, the CoϪC, CoϪP, and PϪC bond lengths are solubility in THF. Their IR spectra display characteristic
close to the average of reported values in arylcobalt com- bands around 1876 cmϪ1 for terminal carbonyl ligands and
pounds. The bond lengths and angles resemble those found around 1539 cmϪ1 for exocyclic CϭN groups; these are
in the unsubstituted parent compound.[8]
hypsochromically shifted by about 18 cmϪ1 with respect to
The bulky CMe3 substituent appears to prevent a close 2 and 3. The 31P NMR spectra show three resonances as
approach of the CHϭN group to the cobalt and causes doublets of doublets which are compatible with trimethyl-
complete switching of the metallation reaction onto the se- phosphane in axial and equatorial positions and an equat-
lective ortho-pathway where the four ortho positions of the orial CO ligand.
PPh2 group are not involved.[2]
The acyl(carbonyl)cobalt complex 7 is soluble in pentane
or diethyl ether. In the IR spectrum the acyl and carbonyl
groups are represented by new bands that fall precisely in
Reactions with Carbon Monoxide
the positions expected for a tbp molecular configuration
with axial acyl and CO ligands.[2] The NMR spectroscopic
data confirm this configuration in solution, and isomers
with equatorial CO ligands are not detected.
An experimental distinction between four- and five-mem-
bered cobaltocycles was achieved by placing solutions of
2Ϫ4 under a pressure of 1 bar CO at 20 °C. While the imino-
acyl complexes 2 and 3 undergo monosubstitution [Equa-
tion (3)], compound 4 takes up two equivalents of CO and
undergoes a ring expansion [Equation (4)].
(4)
(3)
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312
3307

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
Reactions with Ethene
ethene shows the expected increase of 5 pm in the C8ϪC9
bond relative to free ethene. The CoϪC1 and CoϪP bond
lengths fall in the typical range reported for arylcobalt com-
plexes.
Red-brown solutions of 2 or 3 under 1 bar C2H4 turned
orange red within 5 min indicating that a reaction had
taken place [Equation (5)].
When compared with the isoelectronic (2-diphenylphos-
phanyl)benzoyl complex derived from the prechelate system
A, in which cobalt fails to coordinate ethene, the iminoacyl
group places enough electron density on the metal centre
to support olefin binding. As was observed earlier a four-
membered cobaltocycle induces weaker olefin coordina-
tion.[2] Compound 4 forms a π-ethene compound 10 [Equa-
tion (6)] only after thermal pretreatment.
(5)
Short orange rods of 8 or orange rhombs of 9 were ob-
tained from pentane that release ethene while decomposing
above 93 °C under argon. The 31P NMR spectra consist of
three doublets of doublets with JP,P coupling constants of
between 24 and 36 Hz, indicating P-nuclei of trimethylphos-
phanes in axial and equatorial positions leaving an equator-
ial position free for coordination of the ethene ligand.
In the crystal 9 has a molecular structure showing the
expected configuration (Figure 3).
(6)
A cobalt atom in the centre of a trigonal bipyramid is
coordinated to an equatorial ethene and two trimethylphos-
phanes in axial and equatorial positions. A five-membered
metallacycle spans the C-axial and P-equatorial positions
with a C7ϪCoϪP1 bite angle of 79.11(9)° and considerable
bending (sum of internal angles ϭ 520.7° as compared with
540° for a planar arrangement). The side-on coordinated
˚
Figure 3. Molecular structure of 9 (ORTEP plot with hydrogen atoms omitted); selected bond lengths [A] and angles [°]: CoϪC7 2.014(3),
CoϪC8 2.055(3), CoϪC9 2.046(3), CoϪP1 2.1748(10), CoϪP2 2.2232(12), CoϪP3 2.1985(11), P1ϪC1 1.803(3), C1ϪC6 1.401(4), C6ϪC7
1.507(4), C8ϪC9 1.397(5); C7ϪCoϪP1 79.11(9), C7ϪCoϪP2 173.14(9), C7ϪCoϪP3 87.17(9), P1ϪCoϪP2 95.40(4), P1ϪCoϪP3
113.32(4), P2ϪCoϪP3 98.84(4), CoϪC7ϪC6 114.3(2), C1ϪC6ϪC7 114.3(3), C6ϪC1ϪP1 110.4(2)
3308
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312

Schiff-Base Complexes of Cobalt(I)
FULL PAPER
The orange crystals of 10 are readily soluble in diethyl
ether or pentane. Before melting under argon at 105Ϫ107 As the iminoacyl group remains uncoordinated, it retains
°C with decomposition they turn red brown. This behaviour an E-configuration.
indicates a tetracoordinate intermediate which, however,
could not be isolated as an analytically pure compound.
The spectroscopic data of 10 are in agreement with an over-
all replacement reaction of one equatorial trimethylphos-
phane ligand by ethene.
Experimental Section
General Procedures and Materials: All air-sensitive and volatile
materials were handled using standard vacuum techniques and
were kept under argon. Microanalyses: Kolbe Microanalytical
Laboratory, Mülheim/Ruhr, Germany. Melting points/decomposi-
tion temperatures: Sealed capillaries, uncorrected values. Chemicals
(Merck/Schuchardt) were used as purchased. Literature methods
Reactions with Iodomethane
Complexes 2 and 3 react with two molar equivalents of
iodomethane in tetrahydrofuran [Equation (7)] to form the
iodocobalt() complexes 11 and 12 with formal loss of a were followed in the preparation of 2-(diphenylphosphanyl)-
benzaldehyde,[9,10]
2-(diphenylphosphanyl)-N-alkyliminobenzal-
methyl group.
dehyde,[5,11] and [CoMe(PMe3)4].[12] IR: Nujol mulls between KBr
discs, Bruker spectrophotometer type FRA 106. 1H and 13C NMR
spectra (300 MHz and 75 MHz, respectively) were recorded with a
Bruker ARX-300 spectrometer, 31P NMR spectra (81 MHz) with a
Bruker AM-200 instrument. 13C and 31P resonances were obtained
with broad-band proton decoupling. Magnetic susceptibility data
were obtained by the Faraday method using a Cahn D 200 torsion
balance (Bruker) at 1.5 Tesla.
(7)
[(E,Z)-2-(Diphenylphosphanyl)-N-ethylbenzimino-C,P]tris-
(trimethylphosphane)cobalt(I) (1): 2-(Diphenylphosphanyl)-N-ethyl-
benzimide (377 mg, 1.18 mmol) in 30 mL of THF was combined at
Ϫ70 °C with [CoMe(PMe3)4] (450 mg, 1.18 mmol) in 80 mL of
THF. During warm-up evolution of gas was noticed and the mix-
ture became red brown. The mixture was kept at 20 °C for 18 h.
The volatiles were then removed in vacuo, and the solid residue
was extracted with two 70 mL portions of pentane. The solution
was cooled to Ϫ27 °C to afford dark crystals of 1. Yield 322 mg
(45%); m.p. 109Ϫ111 °C (dec.). IR (Nujol): ν˜ ϭ 1542 cmϪ1 (Cϭ
N). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.89 (br. s, 9 H,
Dark brown crystals with a magnetic moment of 1.98
were obtained. A diamagnetic cobalt() intermediate as de-
scribed earlier[2] could not be isolated from reactions in less
polar diethyl ether or pentane solvents.
This particular reactivity has been observed with type A
systems where structural proof of a tbp molecular structure
was obtained with acyl and iodo groups in axial positions.[1]
On the basis of their mutual trans-influences a trans-ar-
rangement of the iminoacyl and iodo ligands would suggest
itself also for 11 and 12.
Under otherwise similar conditions 4 oxidatively adds
iodomethane with substitution and quaternization of a tri-
methylphosphane ligand [Equation (8)].The dark red crys-
tals of 13 melt at 117Ϫ119 °C with decomposition and with
no indication of the formation of a paramagnetic iodocob-
alt() complex as an intermediate. Solutions in THF slowly
decompose at 273 K, but at 203 K the 31P NMR spectro-
scopic data confirm a mer-trans arrangement of the six li-
gand functions.
3
PCH3), 1.18 (br. s, 18 H, PCH3), 1.29 (t, J ϭ 6.9 Hz, 3 H, CH3),
3
3
3.65 (q, J ϭ 6.9 Hz, 2 H, CH2), 6.90 (t, J ϭ 7.2 Hz, 1 H, CH),
7.01 (t, 3J ϭ 7.3 Hz, 1 H, CH), 7.18Ϫ7.29 (m, 8 H, CH), 7.47Ϫ7.53
(m, 4 H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ
17.9 (s, CH3), 23.0 (m, PCH3), 24.8 (m, PCH3), 50.5 (s, CH2), 123.4
2
2
(d, JP,C ϭ 17.8 Hz, CH), 125.8, 126.2 (s, CH), 128.1 (d, JP,C
ϭ
7.2 Hz, CH), (s, CH), 131.1 (s, CH), 133.8 (d, 2JP,C ϭ 12.2 Hz, CH),
142.2 (s, C) ppm. 31P NMR (81 MHz, [D8]THF, 203 K): E-1 (88%)
2
2
δ ϭ Ϫ1 (dd, JP,P ϭ 84 and 44 Hz, 2 P, PCH3), 18 (dd, JP,P ϭ 45
and 44 Hz, 1 P, PCH3), 57 (dt, JP,P ϭ 84 and 45 Hz, 1 P, PPh2);
2
2
Z-1 (12%) δ ϭ Ϫ6 (dd, JP,P ϭ 95 and 63 Hz, 2 P, PCH3), 12 (dt,
2JP,P ϭ 63 and 15 Hz, 1 P, PCH3), 56 (dt, JP,P ϭ 95 and 15 Hz, 1
2
P, PPh2) ppm. C30H46CoNP4 (603.2): calcd. C 59.70, H 7.68, N
2.32, P 20.53; found C 59.85, H 7.60, N 2.35, P 20.52.
[(Z)-2-(Diphenylphosphanyl)-N-isopropylbenzimino-C,P]tris-
(trimethylphosphane)cobalt(I) (2): 2-(Diphenylphosphanyl)-N-iso-
propylbenzimide (622 mg, 1.87 mmol) was combined with [Co-
Me(PMe3)4] (710 mg, 1.87 mmol) as described above to afford dark
red crystals of 2. Yield 683 mg (59%); m.p. 109Ϫ111 °C (dec.). IR
(Nujol): ν˜ ϭ 1520 cmϪ1 (CϭN). 1H NMR (300 MHz, [D8]THF,
(8)
2
296 K): δ ϭ 0.99 (d, JP,H ϭ 6.1 Hz, 9 H, PCH3), 1.29 (d, 3J ϭ
5.9 Hz, 6 H, CH3), 1.12 (br. s, 18 H, PCH3), 4.20 (septet, 3J ϭ
3
3
5.9 Hz, 1 H, CH), 3.65 (q, J ϭ 6.9 Hz, 2 H, CH2), 6.88 (dt, J ϭ
4
3
4
5.9, J ϭ 1.5 Hz, 1 H, CH), 6.98 (dt, J ϭ 5.9, J ϭ 1.5 Hz, 1 H,
CH), 7.08 (m, 2 H, CH), 7.20Ϫ7.22 (m, 6 H, CH), 7.77Ϫ7.84 (m,
4 H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 21.4
(m, PCH3), 23.9 (s, CH3), 53.5 (s, CMe2), 120.4 (d, 1JP,C ϭ 17.2 Hz,
The steric influence of the alkylimino group in 13 does
not affect the coordination sphere of cobalt, therefore the
stereoselective oxidative cis-addition proceeds with reten-
3
CH), 123.6, 123.9 (s, CH), 126.2 (d, JP,C ϭ 7.2 Hz, CH), 128.6 (s,
tion of the metallacycle, as with other ring substituents.[1] C), 132.1 (d, JP,C ϭ 11.8 Hz, CH) ppm. 31P NMR (81 MHz,
2
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312
3309

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
[D8]THF, 203 K): δ ϭ Ϫ4 (dd, JP,P ϭ 79 and 45 Hz, 2 P, PCH3), P, PCH3), 21 (dd, 2JP,P ϭ 53 and 36 Hz, 1 P, PCH3), 68 (dd, 2JP,P ϭ
FULL PAPER
2
2
2
17 (dd, JP,P ϭ 45 and 44 Hz, 1 P, PCH3), 55 (dt, JP,P ϭ 79 and 63 and 36 Hz, 1 P, PPh2) ppm. C29H39CoNOP3 (569.2): calcd. C
44 Hz, 1 P, PPh2) ppm. C31H48CoNP4 (617.2): calcd. C 60.29, H
7.83, N 2.27, P 20.06; found C 59.95, H 7.40, N 2.26, P 20.43.
61.16, H 6.90, N 2.46, P 16.32; found C 60.97, H 6.87, N 2.45,
P 16.20.
[(E)-2-(Diphenylphosphanyl)-N-cyclohexylbenzimino-C,P]tris-
[(E)-2-(Diphenylphosphanyl)-N-cyclohexylbenzimino-C,P]-
(trimethylphosphane)cobalt(
I)
(3): 2-(Diphenylphosphanyl)-N-
carbonylbis(trimethylphosphane)cobalt(I) (6): Carbonylation of 3
cyclohexylbenzimide (790 mg, 2.08 mmol) was combined with (510 mg, 0.77 mmol) in 50 mL of diethyl ether was carried out as
[CoMe(PMe3)4] (775 mg, 2.08 mmol) as described above to afford
in the preparation of 5 to afford 6 as a yellow solid. Yield 449 mg
dark red crystals of 3. Yield 1070 mg (78%); m.p. 113Ϫ115 °C (95%); m.p. 165Ϫ167 °C (dec.). IR (Nujol): ν˜ ϭ 1880 cmϪ1 (CϵO),
(dec.). IR (Nujol): ν˜ ϭ 1527 cmϪ1 (CϭN). 1H NMR (300 MHz, 1540 cmϪ1 (CϭN). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ
[D8]THF, 296 K): δ ϭ 0.98 (br. s, 9 H, PCH3), 1.18 (br. s, 18 H,
1.04 (br. s, 18 H, PCH3), 1.26Ϫ1.86 (m, 10 H, CH2), 3.99 (m, 1 H,
PCH3), 1.34Ϫ1.84 (m, 10 H, CH2), 3.90 (m, 1 H, CH), 6.90 (t, 3J ϭ NCH), 7.04 (m, 2 H, CH), 7.29Ϫ7.31 (m, 8 H, CH), 7.41Ϫ7.43 (m,
7.1 Hz, 1 H, CH), 7.00 (t, 3J ϭ 7.0 Hz, 1 H, CH), 7.05 (m, 2 H,
2 H, CH), 8.00Ϫ8.03 (m, 2 H, CH) ppm. 13C NMR (75.4 MHz,
CH), 7.21Ϫ7.31 (m, 6 H, CH), 7.61Ϫ7.95 (m, 4 H, CH) ppm. 13C [D8]THF, 296 K): δ ϭ 21.9 (m, PCH3), 24.7, 25.2, 26.8, 34.5 (s,
2
NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 21.4 (m, PCH3), 23.2, CH2), 68.8 (s, NCH), 125.5 (d, JP,C ϭ 16.5 Hz, CH), 128.2 (d,
1
2
25.2, 30.9, 34.3 (s, CH2), 60.2 (s, NCH), 120.6 (d, JP,C ϭ 17.3 Hz, 3JP,C ϭ 3.9 Hz, CH), 128.7 (s, CH), 129.1 (d, JP,C ϭ 7.1 Hz, CH),
CH), 123.6, 124.0 (s, CH), 126.3 (d, 3JP,C ϭ 7.1 Hz, CH), 127.3 (d,
133.8 (m, C) ppm. 31P NMR (81 MHz, [D8]THF, 203 K): δ ϭ Ϫ4
2
2
2
2JP,C ϭ 12.2 Hz, CH), 128.8, 130.9 (s, C), 131.1 (d, JP,C ϭ 9.5 Hz, (dd, JP,P ϭ 61 and 54 Hz, 1 P, PCH3), 21 (dd, JP,P ϭ 54 and
2
2
CH), 132.1 (d, JP,C ϭ 11.9 Hz, CH) ppm. 31P NMR (81 MHz, 39 Hz, 1 P, PCH3), 69 (dd, JP,P ϭ 61 and 39 Hz, 1 P, PPh2) ppm.
2
[D8]THF, 203 K): δ ϭ Ϫ4 (dd, JP,P ϭ 80 and 44 Hz, 2 P, PCH3),
C32H43CoNOP3 (609.2): calcd. C 63.05, H 7.11, N 2.30, P 15.24;
2
2
16 (dd, JP,P ϭ 45 and 44 Hz, 1 P, PCH3), 56 (dt, JP,P ϭ 80 and found C 61.62, H 6.35, N 2.06, P 16.49. (Crystals of the analytical
45 Hz, 1 P, PPh2) ppm. C34H52CoNP4 (657.2): calcd. C 62.10, H
7.97, N 2.13, P 18.84; found C 62.22, H 7.41, N 2.10, P 19.09.
sample contained ca. 3% of trimethylphosphane oxide.)
[(E)-2-(Diphenylphosphanyl)benzoyl-3-N-tert-butylimidomethyl-
C,P]carbonylbis(trimethylphosphane)cobalt(I) (7): A sample of 4
[(E)-2-(Diphenylphosphanyl)-N-tert-butylbenzimide-C1,P]tris-
(trimethylphosphane)cobalt(
tylbenzimide (530 mg, 1.50 mmol) in 50 mL of THF was combined
I
) (4): 2-(Diphenylphosphanyl)-tert-bu-
(520 mg, 0.82 mmol) in 70 mL of diethyl ether was kept stirring
under 1 bar of CO for 1 h during which time the colour of the
at Ϫ70 °C with [CoMe(PMe3)4] (570 mg, 1.50 mmol) in 50 mL of mixture turned from red brown to orange. The volatiles were re-
THF and a gas evolved. After 16 h at 20 °C all volatiles were re-
moved from the mixture in vacuo, and the solid residue was ex-
moved in vacuo, and the solid residue was extracted with two
50 mL portions of pentane. Crystallization at Ϫ27 °C afforded dark
tracted with 80 mL of pentane. From the solution 250 mg of dark red rhombs of 7. Yield 380 mg (75%); m.p. 123Ϫ125 °C (dec.). IR
red rhombic crystals were obtained which proved suitable for X-
ray diffraction. Upon cooling to Ϫ27 °C a second fraction of 4 was
collected and combined with the first. Yield 790 mg (83%); m.p.
(Nujol): ν˜ ϭ 1906 cmϪ1 (CϵO), 1630 cmϪ1 (CϭN), 1540 cmϪ1
1
(CϭO). H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.76 (s, 9 H,
CH3), 1.04 (tЈ, |2JP,H
ϩ
4JP,H| ϭ 7.3 Hz, 18 H, PCH3], 7.28Ϫ7.34
1
3
114Ϫ116 °C (dec.). IR (Nujol): ν˜ ϭ 1625 cmϪ1 (CϭN). H NMR
(m, 6 H, CH), 7.46 (dt, J ϭ 7.6, 4J ϭ 2.6 Hz, 1 H, CH), 7.54 (dd,
(300 MHz, [D8]THF, 296 K): δ ϭ 0.91 (s, 9 H, CH3), 1.11 (d, 3J ϭ 6.4, 4J ϭ 1.6 Hz, 1 H, CH) ppm. 13C NMR (75.4 MHz,
4
2JP,H ϭ 6.4 Hz, 9 H, PCH3), 1.28 (tЈ, |2JP,H ϩ JP,H| ϭ 4.7 Hz, 18 [D8]THF, 296 K): δ ϭ 17.9 (m, PCH3), 27.8 (s, CH3), 56.1 (s,
H, PCH3), 6.70 (t, 3J ϭ 7.4 Hz, 1 H, CH), 6.90 (m, 1 H, CH), 7.13
CMe3), 68.8 (s, NCH), 125.5 (d, JP,C ϭ 20.5 Hz, CH), 126.8 (s,
2
(d, 3J ϭ 7.0 Hz, 1 H, CH), 7.25Ϫ7.30 (m, 6 H, CH), 7.74Ϫ7.82 CH), 127.3 (d, 3JP,C ϭ 8.8 Hz, CH), 129.8 (d, 2JP,C ϭ 11.4 Hz, CH),
(m, 4 H, CH), 7.95 (s, 1 H, NCH) ppm. 13C NMR (75.4 MHz, 137.1 (s, C), 138.5 (d, JP,C ϭ 30.7 Hz, CH), 139.7 (d, JP,C
ϭ
1
2
[D8]THF, 296 K): δ ϭ 21.7Ϫ22.9 (m, PCH3), 27.3 (s, CH3), 55.6 (s, 23.9 Hz, CH), 153.3 (s, C), 159.1 (s, NCH) ppm. 31P NMR
3
2
CMe3), 115.4 (s, CH), 126.5 (d, JP,C ϭ 7.8 Hz, CH), 126.8, 127.5 (81 MHz, [D8]THF, 233 K): δ ϭ 9 (d, JP,P ϭ 79 Hz, 1 P, PCH3),
2
2
(s, CH), 131.7 (d, JP,C ϭ 12.9 Hz, CH), 138.0, 138.6 (s, C), 152.2
79 (t, JP,P ϭ 79 Hz, 1 P, PPh2) ppm. C31H41CoNO2P3 (611.2):
2
(d, JP,C ϭ 6.9 Hz, NCH) ppm. 31P NMR (81 MHz, [D8]THF, calcd. C 60.89, H 6.76, N 2.29, P 15.20; found C 61.03, H 7.52, N
2
233 K): δ ϭ Ϫ28 (dt, JP,P ϭ 90 and 71 Hz, 1 P, PPh2), Ϫ3 (dd,
2.28, P 14.85.
2
2JP,P ϭ 90 and 48 Hz, 2 P, PCH3), 21 (dt, JP,P ϭ 71 and 48 Hz, 1
[(E)-2-(Diphenylphosphanyl)-N-isopropylbenzimino-C,P]ethenebis-
P, PCH3) ppm. C32H50CoNP4 (631.2): calcd. C 60.86, H 7.98, N
2.22, P 19.62; found C 60.55, H 7.98, N 2.21, P 19.98.
(trimethylphosphane)cobalt(
I)
(8):
A
sample of
2
(650 mg,
1.05 mmol) in 50 mL of diethyl ether was kept stirring under 1 bar
of C2H4 for 30 min to form an orange solution. The volatiles were
removed in vacuo, and the solid residue was extracted with two
50 mL portions of pentane. Crystallization at Ϫ27 °C afforded or-
[(E)-2-(Diphenylphosphanyl)-N-isopropylbenzimino-C,P]carbonylbis-
(trimethylphosphane)cobalt(
I)
(5):
A sample of 2 (430 mg,
0.69 mmol) in 70 mL of diethyl ether was kept stirring under 1 bar
of CO for 30 min to form a light yellow precipitate. The volatiles ange crystals of 8. Yield 365 mg (61%); m.p. 105Ϫ107 °C (dec.).
were then removed in vacuo, and the solid residue of 5 was washed
with 20 mL of cold diethyl ether and dried in vacuo. Yield 368 mg
(93%); m.p. 185Ϫ187 °C (dec.). IR (Nujol): ν˜ ϭ 1874 cmϪ1 (CϵO),
IR (Nujol): ν˜ ϭ 1541 cmϪ1 (CϭN). 1H NMR (300 MHz, [D8]THF,
2
296 K): δ ϭ 0.69 (d, JP,H ϭ 6.2 Hz, 9 H, PCH3), 1.02 (d, 3J ϭ
2
5.9 Hz, 6 H, CH3), 1.10 (d, JP,H ϭ 6.1 Hz, 9 H, PCH3), 1.67 (m,
2
1538 cmϪ1 (CϭN). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 2 H, CCH2), 2.25 (m, 2 H, CCH2), 3.98 (septet, JP,H ϭ 6.2 Hz, 1
1.05 (br. s, 18 H, PCH3), 1.30 (m, 6 H, CH3), 4.30 (m, 1 H, NCH), H, NCH), 6.79 (dd, 3J ϭ 5.7, 4J ϭ 1.4 Hz, 1 H, CH), 6.93 (dd,
7.09 (m, 2 H, CH), 7.29Ϫ7.31 (m, 8 H, CH), 7.43Ϫ7.58 (m, 2 H, 3J ϭ 7.5, 4J ϭ 1.4 Hz, 1 H, CH), 7.03 (m, 1 H, CH), 7.26Ϫ7.30
CH), 8.22Ϫ8.28 (m, 2 H, CH) ppm. 13C NMR (75.4 MHz, (m, 6 H, CH), 7.74Ϫ7.83 (m, 4 H, CH) ppm. 13C NMR (75.4 MHz,
1
[D8]THF, 296 K): δ ϭ 19.9 (m, PCH3), 23.1 (s, CH3), 8.5 (s, NCH), [D8]THF, 296 K): δ ϭ 17.5 (d, JP,C ϭ 13.3 Hz, PCH3), 21.1 (d,
2
2
2
127.5 (d, JP,C ϭ 16.5 Hz, CH), 128.2 (d, JP,C ϭ 15.9 Hz, CH),
1JP,C ϭ 23.0 Hz, PCH3), 23.9 (s, CH3), 48.2 (d, JP,C ϭ 20.4 Hz,
2
2
129.1 (d, JP,C ϭ 7.0 Hz, CH), 143.1 (m, C) ppm. 31P NMR CCH2), 52.1 (d, JP,C ϭ 13.9 Hz, CCH2), 54.1 (s, NCH), 122.5 (d,
2
(81 MHz, [D8]THF, 203 K): δ ϭ Ϫ4 (dd, JP,P ϭ 63 and 53 Hz, 1
2JP,C ϭ 15.2 Hz, CH), 126.8 (s, CH), 127.9Ϫ134.0 (s, CH), 134.9
3310
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312

Schiff-Base Complexes of Cobalt(I)
FULL PAPER
[(E)-2-(Diphenylphosphanyl)-N-isopropylbenzimino-C,P]iodobis-
2
2
(d, JP,C ϭ 12.1 Hz, CH), 138.3 (m, CH), 139.2 (d, JP,C ϭ 9.6 Hz,
1
CH), 140.2 (d, JP,C ϭ 22.4 Hz, CH) ppm. 31P NMR (81 MHz, (trimethylphosphane)cobalt(II
)
(11):
A sample of 2 (850 mg,
[D8]THF, 203 K): δ ϭ 8 (dd, 2JP,P ϭ 30 and 26 Hz, 1 P, PCH3), 16 1.37 mmol) in 50 mL of THF at Ϫ70 °C was combined with iodo-
2
2
(dd, JP,P ϭ 30 and 36 Hz, 1 P, PCH3), 67 (dd, JP,P ϭ 36 and
26 Hz, 1 P, PPh2) ppm. C30H43CoNP3 (569.2): calcd. C 63.27, H
7.61, N 2.46, P 16.32; found C 63.40, H 7.80, N 2.41, P 15.80.
methane (488 mg, 3.44 mmol). After 3 h at 20 °C an off-white solid
of tetramethylphosphonium iodide (IR) was filtered off, and the
filtrate was evaporated to dryness. Extraction with three 80 mL
portions of diethyl ether and cooling to 4 °C afforded dark brown
platelets of 11. Yield 440 mg (48%); m.p. 130Ϫ132 °C (dec.). IR
(Nujol): ν˜ ϭ 1554 cmϪ1 (CϭN). Magnetic moment: µeff ϭ 1.98 µB.
C28H39CoINP3 (668.1): calcd. C 50.32, H 5.88, N 2.10, P 13.90;
found C 50.56, H 6.58, N 2.02, P 13.88.
[(E)-2-(Diphenylphosphanyl)-N-cyclohexylbenzimino-C,P]ethenebis-
(trimethylphosphane)cobalt(
I)
(9):
A sample of 3 (680 mg,
1.03 mmol) in 50 mL of pentane was kept stirring under 1 bar of
C2H4 for 20 min to form a yellow solid. The supernatant solution
was decanted and kept at Ϫ4 °C to afford yellow crystals of 9.
The solid was recrystallised from pentane. Combined yields 460 mg
(73%); m.p. 93Ϫ95 °C (dec.). IR (Nujol): ν˜ ϭ 1557 cmϪ1 (CϭN).
1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.66 (d, 2JP,H ϭ 6.3 Hz,
[(E)-2-(Diphenylphosphanyl)-N-cyclohexylbenzimino-C,P]iodobis-
(trimethylphosphane)cobalt(II
) (12): A sample of 3 (790 mg,
1.20 mmol) in 80 mL of THF at Ϫ70 °C was combined with iodo-
methane (375 mg, 2.64 mmol). After 3 h at 20 °C workup pro-
ceeded as in the preparation of 11 to afford dark brown platelets
of 12. Yield 505 mg (63%); m.p. 128Ϫ134 °C (dec.). IR (Nujol):
ν˜ ϭ 1547 cmϪ1 (CϭN). Magnetic moment: µeff ϭ 1.98 µB.
C31H43CoINP3 (708.1): calcd. C 52.56, H 6.12, N 1.98, P 13.12;
found C 52.60, H 5.74, N 1.98, P 12.58.
3
9 H, PCH3), 1.07 (d, J ϭ 6.1 Hz, 9 H, PCH3), 1.24Ϫ1.99 (m, 10
H, CH2), 1.80 (m, 2 H, CCH2), 2.19 (m, 2 H, CCH2), 3.41 (septet,
3JP,H ϭ 3.8 Hz, 1 H, NCH), 6.83 (dd, J ϭ 5.5, J ϭ 1.5 Hz, 1 H,
3
4
3
4
CH), 7.00 (dt, J ϭ 7.3, J ϭ 1.5 Hz, 1 H, CH), 7.26Ϫ7.30 (m, 6
H, CH), 7.34 (dt, 3J ϭ 5.2, 4J ϭ 0.9 Hz, 1 H, CH), 7.44 (ddd, 3J ϭ
5.7, 5.0, J ϭ 1.1 Hz, 2 H, CH), 7.98 (ddd, J ϭ 9.5, J ϭ 1.9, 1.5
Hz, 2 H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ
4
3
4
mer-trans-[(E)-2-(Diphenylphosphanyl)-N-tert-butylbenzimide-
C1,P]iodo(methyl)bis(trimethylphosphane)cobalt(III) (13): A sample
of 4 (920 mg, 1.45 mmol) in 50 mL of diethyl ether at Ϫ70 °C was
combined with excess iodomethane (455 mg, 3.20 mmol). After 1 h
at 20 °C the solution became red. An off-white solid of tetramethyl-
phosphonium iodide was filtered off, and the solution at 4 °C af-
forded red crystals of 13. Yield 518 mg (51%); m.p. 117Ϫ119 °C
(dec.). IR (Nujol): ν˜ ϭ 1633 cmϪ1 (CϭN). 1H NMR (300 MHz,
[D8]THF, 296 K): δ ϭ 0.54 (m, 3 H, CoCH3), 0.80 (s, 9 H, CCH3),
1.04 (br. s, 18 H, PCH3), 7.51Ϫ7.56 (m, 6 H, CH), 7.74Ϫ7.79 (m, 4
H, CH), 8.20 (s, 1 H, NCH) ppm. 13C NMR (75.4 MHz, [D8]THF,
1
1
18.0 (d, JP,C ϭ 13.2 Hz, PCH3), 20.6 (d, JP,C ϭ 22.8 Hz, PCH3),
2
24.9, 25.2, 27.2, 35.2, 36.0 (s, CH2), 48.3 (d, JP,C ϭ 18.4 Hz,
2
CCH2), 51.5 (d, JP,C ϭ 11.3 Hz, CCH2), 60.3 (s, NCH), 122.5 (d,
3JP,C ϭ 16.0 Hz, CH), 125.1 (d, 4JP,C ϭ 4.4 Hz, CH), 126.8 (s, CH),
128.0 (d, 3JP,C ϭ 8.7 Hz, CH), 128.5 (d, 3JP,C ϭ 7.6 Hz, CH), 129.1
3
2
(d, JP,C ϭ 8.6 Hz, CH), 134.5 (d, JP,C ϭ 10.1 Hz, CH), 134.9 (d,
2JP,C ϭ 12.1 Hz, CH), 138.8 (d, JP,C ϭ 9.8 Hz, CH), 139.2 (d,
2
2JP,C ϭ 9.6 Hz, CH), 141.1 (d, 1JP,C ϭ 22.8 Hz, C], 146.7 (d, 1JP,C ϭ
1
2
44.9 Hz, C), 156.4 (dd, JP,C ϭ 43.5, JP,C ϭ 10.4 Hz, NC) ppm.
31P NMR (81 MHz, [D8]THF, 203 K): δ ϭ 7 (dd, JP,P ϭ 30 and
2
2
24 Hz, 1 P, PCH3), 16 (dd, JP,P ϭ 30 and 36 Hz, 1 P, PCH3), 66
(dd, JP,P ϭ 36 and 24 Hz, 1 P, PPh2) ppm. C33H47CoNP3 (609.2):
2
calcd. C 65.02, H 7.77, N 2.30, P 15.24; found C 64.79, H 7.39, N
2.22, P 15.30.
Table 1. Crystal data for compounds 4 and 9
[(E)-2-(Diphenylphosphanyl)-N-tert-butylbenzimide-C1,P]ethenebis-
(trimethylphosphane)cobalt(I) (10): A sample of 4 (640 mg,
4
9
1.01 mmol) was kept at 100 °C in vacuo for 5 h. After cooling
30 mL of diethyl ether was condensed upon the red brown solid,
and at 20 °C the solution was kept stirring under 1 bar of ethene
for 1 h. The volatiles were removed in vacuo, and the solid residue
was extracted with two 30 mL portions of pentane. Crystallization
at Ϫ4 °C afforded orange crystals of 10. Yield 236 mg (40%); m.p.
Empirical formula
Molecular mass
Crystal size [mm]
Crystal system
Space group
C32H50CoNP4
631.5
0.48 ϫ 0.42 ϫ 0.30 0.52 ϫ 0.30 ϫ 0.26
monoclinic
P21/n
13.950(2)
18.288(6)
14.056(3)
102.18(1)
3505.2(15)
4
1.197
0.693
293(2)
4.4 Յ 2Θ Յ 50
Ϫ16 Յ h Յ 0
0 Յ k Յ 21
Ϫ16 Յ l Յ 16
C33H47CoNP3
609.6
monoclinic
P21/c
˚
1
105Ϫ107 °C (dec.). IR (Nujol): ν˜ ϭ 1633 cmϪ1 (CϭN). H NMR
a [A]
14.930(4)
12.674(3)
18.584(4)
112.04(2)
3259.5(14)
4
1.242
0.696
293(2)
5.5 Յ 2Θ Յ 55
Ϫ1 Յ h Յ 14
Ϫ16 Յ k Յ 1
Ϫ24 Յ l Յ 22
8014
˚
b [A]
(300 MHz, [D8]THF, 296 K): δ ϭ 0.82 (s, 9 H, CH3), 0.90 (d,
2JP,H ϭ 6.3 Hz, 9 H, PCH3), 1.05 (d, 3J ϭ 6.2 Hz, 9 H, PCH3),
1.61 (m, 2 H, CCH2), 1.80 (m, 2 H, CCH2), 5.99 (m, 1 H, CH),
6.44 (m, 1 H, CH), 6.75 (dt, 3J ϭ 7.5, 4J ϭ 2.0 Hz, 1 H, CH),
7.17Ϫ7.19 (m, 3 H, CH), 7.29 (s, 1 H, NCH), 7.34Ϫ7.36 (m, 3 H,
CH), 7.71Ϫ7.77 (m, 2 H, CH), 7.92Ϫ7.98 (m, 2 H, CH) ppm. 13C
˚
c [A]
β [°]
3
˚
V [A ]
Z
Dcalcd. [g/cm3]
µ(Mo-Kα) [mmϪ1
]
1
NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 16.8 (d, JP,C ϭ 17.9 Hz,
Temperature [K]
1
PCH3), 19.1 (d, JP,C ϭ 17.9 Hz, PCH3), 24.9 (s, CH3), 25.2 (s, Data coll. range [°]
h
k
l
CMe3), 33.2 (m, CCH2), 35.3 (m, CCH2), 109.5 (s, CH), 125.8 (d,
2JP,C ϭ 15.6 Hz, C), 126.6 (d, 3JP,C ϭ 7.9 Hz, CH), 126.8 (d, 2JP,C ϭ
2
8.4 Hz, CH), 127.2, 128.8 (s, CH), 132.1 (d, JP,C ϭ 12.3 Hz, CH),
No. reflect. measured 6439
2
132.9 (d, JP,C ϭ 12.6 Hz, CH), 169.1 (s, NCH) ppm. 31P NMR
No. unique data
Parameters
6171 [Rint ϭ 0.0310] 6551 [Rint ϭ 0.0205]
394
0.982
0.0536
0.1215
2
(81 MHz, [D8]THF, 203 K): δ ϭ Ϫ21 (dd, JP,P ϭ 51 and 47 Hz, 1
356
2
2
P, PPh2), 9 (dd, JP,P ϭ 47 and 32 Hz, 1 P, PCH3), 17 (dd, JP,P
ϭ
GoF on F2
1.045
0.0419
0.1094
32 and 51 Hz, 1 P, PCH3) ppm. C31H45CoNP3 (583.2): calcd. C
63.81, H 7.77, N 2.40, P 15.92; found C 63.46, H 7.30, N 2.36,
P 16.48.
R1 [I Ն 2σ(I)]
wR2 (all data)
Eur. J. Inorg. Chem. 2002, 3305Ϫ3312
3311

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
296 K): δ ϭ 16.9 (m, PCH3), 28.2 (s, CH3), 56.6 (s, CMe3), 121.5
Acknowledgments
2
(d, JP,C ϭ 11.5 Hz, C), 126.5 (s, CH), 128.4 (s, CH), 129.6 (d,
Financial support of this work by Fonds der Chemischen Industrie
is gratefully acknowledged.
2JP,C ϭ 11.4 Hz, CH), 137.1 (s, C), 138.2 (s, C), 139.5 (m, C), 160.1
(s, NCH) ppm. 31P NMR (81 MHz, [D8]THF, 203 K): δ ϭ Ϫ34 (t,
2
2JP,P ϭ 25 Hz, 1 P, PPh2), 11 (d, JP,P ϭ 25 Hz, 2 P, PCH3) ppm.
[1]
H.-F. Klein, U. Lemke, M. Lemke, A. Brand, Organometallics
C30H44CoINP3 (697.1): calcd. C 51.66, H 6.36, N 2.10, P 13.32;
found C 51.65, H 6.52, N 1.98, P 13.26.
1998, 17, 4196Ϫ4201.
H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt, Eur. J. Inorg.
[2]
Chem. 2002, in press.
H. Brunner, P. Faustmann, A. Dieth, B. Nuber, J. Organomet.
[3]
Chem. 1997, 542, 255Ϫ283.
Crystal Structure Analyses: Crystal data are presented in Table 1.
Data collection: Complex 4: A crystal was sealed under argon in a
glass capillary and mounted on a Bruker AXS P4 diffractometer.
Reflections were collected (ω-scans) using graphite monochrom-
ated Mo-Kα radiation; a Lorentz polarisation and an absorption
correction based on psi-scans were applied. The structure was
solved by direct and conventional Fourier methods. All non-hydro-
gen atoms were treated anisotropically, hydrogen atoms were
treated with a riding model in idealised positions. The tBu group
as well as the P(4)Me3 group are disordered over four positions
along the N(1)ϪC(8) axis and the Co(1)ϪP(4) axis, respectively.
These positions were refined with split models. Resulting site occu-
pation factors for the 4 tBu positions are 0.24(2), 0.24(2), 0.34(3),
and 0.18(2); site occupation factors for the 4 PMe3 positions are
0.26(2), 0.13(1), 0.36(2), and 0.25(2). Complex 9: Crystal mounting,
data collection, structure solution, and refinement as for 4.
[4]
T. B. Rauchfuss, J. Organomet. Chem. 1978, 162, C19ϪC22.
[5]
C. A. Ghilardi, S. Midollini, S. Moneti, A. Orlandini, G. Scap-
pacci, J. Chem. Soc., Dalton Trans. 1992, 3371Ϫ3376.
P. Barbaro, C. Bianchini, F. Laschi, S. Midollini, S. Moneti, G.
[6]
Scappacci, Inorg. Chem. 1994, 33, 1622Ϫ1630.
[7]
J. Ko, W. C. Joo, Y. K. Kong, Bull. Korean Chem. Soc. 1986,
7, 338 Ϫ341.
[8]
H.-F. Klein, S. Schneider, M. He, U. Flörke, H.-J. Haupt, Eur.
J. Inorg. Chem. 2000, 2295Ϫ2301.
[9]
G. P. Schiemenz, A. Kaack, Justus Liebigs Ann. Chem. 1973,
1480Ϫ1493.
[10]
J. E. Hoots, T. B. Rauchfuss, D. A. Wrobleski, Inorg. Synth.
1982, 21, 175Ϫ179.
P. Wehman, H. M. A. van Donge, A. Hagos, P. C. J. Kamer, P.
W. N. M. van Leeuwen, J. Organomet. Chem. 1997, 535,
183Ϫ193.
H.-F. Klein, H. H. Karsch, Chem. Ber. 1975, 108, 944Ϫ954.
[11]
[12]
[13]
´
F. H. Carre, C. Chuit, R. J. P. Corriu, W. E. Douglas, D. M.
´
H. Guy, C. Reye, Eur. J. Inorg. Chem. 2000, 647Ϫ653.
CCDC-184403 (4) and CCDC-184404 (9) contain the supplement-
ary crystallographic data for this paper. These data can be obtained
free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or
from the Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ44Ϫ1223/
336Ϫ033; E-mail: deposit@ccdc.cam.ac.uk].
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Received June 27, 2002
[I02353]
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Eur. J. Inorg. Chem. 2002, 3305Ϫ3312