Fluxional and rigid (trimethylphosphane)cobalt complexes containing chelating (2-diphenylphosphanyl)anilido ligands

Article abstract of DOI:10.1002/ejic.200390032

2-(Diphenylphosphanyl)anilines (P/NHR) eliminate methane upon reaction with [CoMe(PMe_3])₄] forming the complexes [Co(η²-P/NR)(PMe₃)₃] (1: R = H; 2: R = Me) and [Co(η²- P/NR)(PMe₃)₂] (3: R = Me). Reaction with HCl gives [CoCl(η¹-P/NHR)(PMe₃)₂] (4: R = H; 5: R = Me) and reaction with CO or olefin gives [Co(η²-P/NR)(CO)(PMe₃)₂] (6: R = H; 7: R = Me) and [Co(η²-P/NR)(olefin)(PMe₃)₂] (8: R = H, olefin = C₂H₄; 9: R = Me, olefin = C₂H₄; 10: R = Me, olefin = C₃H₆), respectively. No catalytic transformation of the olefins was observed. Oxidation by iodomethane yields a cobalt(II) compound [CoI(ν²-P/NR)(PMe₃)₂] (11: R = Me). By treating 2 -(diphenylphosphanyl)aniline with [CoMe₂(PMe₃)₃] a methylcobalt(II) complex [CoMe(η²-P/NR)(PMe₃)₂] (12: R = H) is obtained, while an excess of the aniline produces [Co(η²-P/NR)₂] (13: R = H; 14: R = Me) or [Co(η²-P/NR)₂(PMe₃)] (15: R = H; 16: R = Me). The methylcobalt(III) complexes mer-trans-[CoIMe₂(η²-P/NR) (PMe₃)₂] were obtained from LiP/NR and [CoClMe₂(PMe₃)₃]. Dynamic ³¹P NMR spectra and the structures of complexes 3, 6, 12, and 13 are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200390032

FULL PAPER
Fluxional and Rigid (Trimethylphosphane)cobalt Complexes Containing
Chelating (2-Diphenylphosphanyl)anilido Ligands
Hans-Friedrich Klein,*[a] Robert Beck,[a] Ulrich Flörke,[b] and Hans-Jürgen Haupt[b]
Keywords: Chelates / Cobalt / P ligands / Structure elucidation
2-(Diphenylphosphanyl)anilines (P∧NHR) eliminate methane
upon reaction with [CoMe(PMe3)4] forming the complexes
[Co(η2-P∧NR)(PMe3)3] (1: R = H; 2: R = Me) and [Co(η2-
2-(diphenylphosphanyl)aniline with [CoMe2(PMe3)3]
a
methylcobalt(II) complex [CoMe(η2-P∧NR)(PMe3)2] (12: R =
H) is obtained, while an excess of the aniline produces
P∧NR)(PMe3)2] (3:
R
=
Me). Reaction with HCl gives
[Co(η2-P∧NR)2] (13:
R
=
H; 14:
R =
Me) or [Co(η2-
[CoCl(η1-P∧NHR)(PMe3)2] (4: R = H; 5: R = Me) and reaction
with CO or olefin gives [Co(η2-P∧NR)(CO)(PMe3)2] (6: R = H;
7: R = Me) and [Co(η2-P∧NR)(olefin)(PMe3)2] (8: R = H, ol-
efin = C2H4; 9: R = Me, olefin = C2H4; 10: R = Me, olefin =
C3H6), respectively. No catalytic transformation of the olefins
P∧NR)2(PMe3)] (15: R = H; 16: R = Me). The methylcobalt(III
)
complexes mer-trans-[CoIMe2(η2-P∧NR)(PMe3)2] were ob-
tained from LiP∧NR and [CoClMe2(PMe3)3]. Dynamic 31P
NMR spectra and the structures of complexes 3, 6, 12, and
13 are discussed.
was observed. Oxidation by iodomethane yields a cobalt(II
)
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
compound [CoI(η2-P∧NR)(PMe3)2] (11: R = Me). By treating Germany, 2003)
Introduction
Here we describe the synthesis and structural properties
of some novel mononuclear complexes of cobalt() and their
transformation by oxidative addition reactions including an
unexpected cyclometallation reaction.
Molecular derivatives of 2-(diphenylphosphanyl)aniline
are well known as P,N-chelating ligands for the late trans-
ition metals,[1] and palladium(), in particular, has been
extensively investigated regarding certain aspects of homo-
geneous catalysis. Examples of first-row transition metals in
early studies by Venanzi et al.[2] are molecular dihalides of
cobalt and nickel (high-spin) which have a tetrahedral coor-
dination geometry.
Results and Discussion
2-(Diphenylphosphanyl)anilines react with [CoMe-
(PMe3)4] [Equation (1)] with the elimination of methane to
afford the pentacoordinate cobalt() complexes 1 and 2 as
brown solids that are freely soluble in pentane or diethyl
ether.
Vaska-type square-planar complexes of rhodium() and
iridium() containing 2-(diphenylphosphanyl)-N-methyl-
anilido ligands have been investigated by Dahlenburg et
al.,[3] and examples of a µ2-bridging coordination mode of
the 2-(diphenylphosphanyl)anilido ligand have been found
in triangular clusters of ruthenium[4] and osmium.[5]
(1)
[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
240
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0102Ϫ0240 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2003, 240Ϫ248

(Trimethylphosphane)cobalt Complexes Containing Chelating (2-Diphenylphosphanyl)anilido Ligands
FULL PAPER
Complex 1 forms dark brown crystals, while 2 is obtained
as a solid wax, in moderate yield, from pentane containing
excess trimethylphosphane. When dissociation of ligands is
favoured, by applying fresh solvent or warming solid 2 in
vacuo, a gradual transformation to the tetracoordinate
complex 3 is achieved which eventually forms small red
brown rods that are highly air-sensitive but thermally stable
up to 135 °C. The observed magnetic susceptibility (µeff/
µB ϭ 2.97) is typical for tetrahedral complexes of cobalt().
Complexes 1 and 2 show a characteristic pattern of 31P
NMR signals: a doublet of triplets at δ ϭ 52 ppm for the
chelating P nucleus, which experiences a coordination
chemical shift of δ ϭ 70 ppm, a doublet of doublets at δ ϭ
Ϫ7 ppm for two isochronic P nuclei and a doublet of trip-
lets at δ ϭ 28 ppm for a third trimethylphosphane P nuc-
leus (Figure 1).
Figure 2. Molecular structure of 3 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪN1
1.926(2), CoϪP1 2.2374(9), CoϪP2 2.2243(10), CoϪP3 2.2473(12),
P1ϪC11 1.815(3), C11ϪC16 1.426(4), C16ϪN1 1.363(4);
N1ϪCoϪP1 86.34(8), N1ϪCoϪP2 128.00(9), N1ϪCoϪP3
118.97(9), C1ϪN1ϪCo 121.3(2), C16ϪN1ϪCo 122.24(18),
C1ϪN1ϪC16 116.4(3), P1ϪCoϪP2 108.58(4), P1ϪCoϪP3
107.87(4), P2ϪCoϪP3 103.64(4), CoϪP1ϪC11 98.72(9),
P1ϪC11ϪC16 114.4(2)
ing the tetracoordinate complexes 4 and 5 [Equation (2)].
The process can be reversed by treating the compound with
methyllithium. In a most convenient synthesis CoCl(PMe3)3
is treated with the appropriate 2-(diphenylphosphanyl)ani-
line [Equation (3)].
Figure 1. 31P NMR spectrum of 1 (81 MHz, [D8]THF, 233 K)
The values of the coupling constants (J ϭ 99 and 61 Hz)
fall in the range expected for the angles PϪCoϪP
(90Ϫ110°) and suggest a trigonal-bipyramidal coordination
geometry with two trimethylphosphane groups in equator-
ial positions.
(2)
(3)
In the molecular structure of 3 (Figure 2) a tetrahedral
coordination geometry is confirmed by the angles PϪCoϪP
(108Ϫ109°). The chelate bite angle P1ϪCoϪN [86.34(8)°] is
slightly larger than that found in a related pentacoordinate
nickel() complex,[6] and the sum of the internal angles in
the metallacycle (539.9°) equals that of a regular pentagon;
N coordination to the cobalt() ion (16 valence electrons)
[7]
˚
[CoϪN 1.926(2) A] is found to be a normal distance, and
remarkably, the sum of the angles at the nitrogen atom
(359.9°) indicates planarity as is the case in the nickel com-
plex (18 valence electrons).
Complexes 4 and 5 form green solids that are insoluble
in pentane, highly soluble in THF, and are best recrys-
tallised from diethyl ether. IR spectra in the ν(NH) region
show the expected number of bands at 3404 and 3318 cmϪ1
(4) that are close to those of 2-(diphenylphosphanyl)aniline.
A band occurring at 3332 cmϪ1 (5) is shifted by 30 cmϪ1
Reactions
Ethereal HCl protonates the N donor and one of the tri-
methylphosphane groups, thereby opening the chelate ring with respect to 2-(diphenylphosphanyl)-N-methylaniline in-
in 1 or 2 while retaining the Ph2P donor group and generat- dicating an intramolecular hydrogen bond NϪH···Cl in 5.
Eur. J. Inorg. Chem. 2003, 240Ϫ248
241

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
The values of the magnetic susceptibilities (4: µeff/µB ϭ 3.29;
Brown solutions of 1 or 2 in pentane under 1 bar of
5: µeff/µB ϭ 3.25) are consistent for tetrahedral high-spin ethene or propene turn red and upon cooling afford red
complexes.[8] Under 1 bar of CO 1 and 2 smoothly form crystals of monoolefin complexes 8Ϫ10 [Equation (5)], in
monocarbonyl complexes [Equation (4)].
the case of 6 and 7 together with crystals of 3. No reaction
is observed in neat cyclopentene.
(4)
(5)
From pentane, red crystals of 6 and 7 are obtained that
are thermally stable up to 150 °C. IR spectra contain single
ν(CO) bands of terminal carbonyl ligands (6: 1887 cmϪ1; 7:
1906 cmϪ1) indicating that only one of the possible two
isomers is present. The 31P NMR doublet and triplet reson-
ances at characteristic shifts, along with the larger coupling
(J ϭ 97 Hz) indicate that the carbonyl ligand resides in an
axial position. This configuration is also adopted in the
Careful drying under a gas blanket of olefin and manual
selection of crystals gives analytically pure samples of
8Ϫ10. All three compounds are solids with low melting
points that are sensitive towards heat and oxygen, already
releasing olefin at 20 °C in vacuo. As no structural proof
has been obtained by X-ray diffraction on single crystals,
31P NMR spectroscopy was used to support pentacoordin-
ation in compounds 8Ϫ10. At 193 K ligand mobility is slow
enough to reveal the ground-state geometry through a
doublet of doublets pattern of three 31P NMR signals
(Table 1).
Table 1. 31P NMR spectroscopic data (81 MHz, [D8]THF, 193 K)
for (olefin)cobalt compounds 8Ϫ10 [δ in ppm, J in Hz]
δ(PPh
)
)
δ(Pax
)
)
δ(Peq)
)
2J(PPhPeq
2J(PPhPax
)
2J(PaxPPh
2J(PaxPeq
)
2J(PeqPPh
2J(PeqPax
)
8
9
61 (dd)
34
61 (dd)
36
23 (dd)
30
23 (dd)
32
22 (dd)
30
3 (dd)
34
3 (dd)
36
3 (dd)
38
30
32
30
52
56
52
52
56
52
10 61 (dd)
38
31P nuclei of axial and equatorial trimethylphosphane
groups are coupled with an equatorial chelating 31P nucleus
leaving an equatorial position for the olefin ligand. Reac-
tion of 2 with iodomethane [Equation (6)] Ϫ oxidative sub-
stitution of a trimethylphosphane group and quaternisation
Ϫ takes an unexpected course.
Figure 3. Molecular structure of 6 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪC1
1.754(14), C1ϪO2 1.157(15), CoϪP4 2.210(3), CoϪP5 2.184(3),
CoϪP6 2.194(3), CoϪN2 1.907(9), N2ϪC2 1.360(14), C2ϪC3
1.411(15), P4ϪC3 1.80(1); N2ϪCoϪC1 176.9(5), N2ϪCoϪP4
84.3(3), N2ϪCoϪP5 86.1(3), N2ϪCoϪP6 88.2(3), CoϪN2ϪC2
122.6(8),
N2ϪC2ϪC3
118.8(9),
C2ϪC3ϪP4
111.6(8),
C3ϪP4ϪCo 100.6(4)
crystal, as shown by the molecular structure of 6 (Figure 3).
The carbonyl and amide ligands occupy axial positions
with tighter bonding [CoϪN ϭ 1.907(9) A] than that in 3
(6)
˚
which arises from a push-pull stabilisation of ligands in
trans positions [CϪCoϪN 176.9(5)°]. The chelate bite angle
P4ϪCoϪN [84.3(3)°] is only 2° larger than it is in 3, and
the sum of the internal angles in the metallacycle is 537.9°.
Black crystals of an iodocobalt() complex 11 are ob-
There is a close structural correspondence between 6 and a tained from diethyl ether. Elemental analysis shows that the
related carbonylbis(trimethylphosphane)cobalt()(P,O-che- cobalt atom has lost the initial methylmetal function and is
late) complex[9] as can be expected of isoelectronic O and coordinated to five ligands. Accordingly, the magnetic sus-
NH donors.
ceptibility (µeff/µB ϭ 2.09) is as expected for a pentacoordin-
242
Eur. J. Inorg. Chem. 2003, 240Ϫ248

(Trimethylphosphane)cobalt Complexes Containing Chelating (2-Diphenylphosphanyl)anilido Ligands
FULL PAPER
ate cobalt (d7) compound.[10] A corresponding methylco- 3, and the sum of the internal angles (539.9°) indicates a
balt() complex 12 is obtained by reaction of 2-(di- relaxed metallacycle. Reactivity of the methylmetal function
phenylphosphanyl)aniline with CoMe2(PMe3)3 [Equa- is sufficient to afford bis(P,N)chelate compounds of co-
tion (7)].
balt() [Equation (8)].
(7)
(8)
The black crystals of 12 are freely soluble in pentane and
are thermally even more stable than 11. The magnetic sus-
ceptibility (µeff/µB ϭ 1.65) is at the lower end of that ex-
pected for a trigonal-bipyramidal configuration of the Co
atom (d7, 17 valence electrons).[10] While no solution struc-
ture of 12 could be derived from spectroscopic data, the
molecular structure was revealed by X-ray diffraction (Fig-
ure 4).
The molecular complexes 13 and 14 (15 metal valence
electrons) are stable up to 250 and 200 °C, respectively.
Only when additional trimethylphosphane is supplied in ex-
cess, does it coordinate to afford the pentacoordinate spe-
cies 15 and 16. Magnetic susceptibilities (13: µeff/µB ϭ 2.05;
14: µeff/µB ϭ 2.33; 15: µeff/µB ϭ 2.10; 16: µeff/µB ϭ 2.04) fall
in the range expected for tetracoordinate (low-spin)[9,11] and
pentacoordinate[9,10] cobalt() compounds but give no fur-
ther clue to the configuration of the complexes.
In the molecular structure of 13 (Figure 5) a trans square-
planar arrangement of ligands is revealed around a cobalt
atom sitting in a centre of inversion. The chelate bite angle
is normal [PϪCoϪN 83.6(2)°] and so are the bond lengths
˚
[CoϪN 1.858(6), CoϪP 2.212(6) A]. The structure of 13 is
the first for this type of bis(P,N)chelate cobalt complex,
with the trans configuration differing from that of isoelec-
tronic cis-bis(P,O)chelate cobalt compounds.[9]
In an attempted synthesis of methylcobalt() complexes
containing chelating 2-(diphenylphosphanyl)anilido ligands
no reaction of CoMe3(PMe3)3 with 2-(diphenylphos-
phanyl)aniline or 2-(diphenylphosphanyl)-N-methylaniline
was observed. An alternative route [Equation (9)] afforded
the dimethylcobalt() compounds 17 and 18.
Figure 4. Molecular structure of 12 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪC1
2.019(3), CoϪN1 1.929(2), CoϪP1 2.2472(8), CoϪP2 2.1858(9),
CoϪP3 2.2833(8), N1ϪC16 1.351(3), C16ϪC11 1.407(4), C11ϪP1
1.808(3); P1ϪCoϪC1 162.43(10), N1ϪCoϪP2 154.60(7),
N1ϪCoϪP3 102.47(7), N1ϪCoϪP1 82.64(7), CoϪN1ϪC16
125.32(18), N1ϪC16ϪC11 118.5(2), C16ϪC11ϪP1 111.83(19),
C11ϪP1ϪCo 101.65(9)
The cobalt centre of 12 is located above an almost square
plane (P1,P2,C1,N1) with an apical trimethylphosphane
group (P3) attached to it at the longest CoϪP distance. The
void trans to P3 is large enough for, although not occupied
by, a hydride ligand. This is seen from the IR spectrum
where the ν(CoH) region is empty along with the d7 valence
state of the Co atom. The methyl ligand (C1) is arranged
(9)
Highly soluble short orange rods of 17 and 18 are crys-
in the opposite position to the chelating P donor (P1) which tallised from pentane and melt at 85 and 89 °C, respectively.
is different from an otherwise related pentacoordinate Under conditions of low ligand mobility (193 K) the 31P
methylnickel() complex (18 electrons), where it is trans to NMR signals recorded as a triplet (1 P) and doublet (2 P)
the amide donor.[6] The chelate bite angle is close to that in indicate a meridional arrangement of P donor functions in
Eur. J. Inorg. Chem. 2003, 240Ϫ248
243

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
signals of 19 were detected besides some trimethylphos-
phane oxide and the well-known marks of silicon grease,
which amounts to an estimated regioselectivity of better
than 99%.
Complexes of rhodium and iridium, containing 2-(di-
phenylphosphanyl)-N,N-dimethylaniline as a bidentate li-
gand, have been described,[13] and no ortho-metallation was
reported. Clearly, this spontaneous transformation with co-
balt and its unexpected absolute selectivity merit further in-
vestigation.
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, FRG. Melting points/decomposition
temperatures: Sealed capillaries, uncorrected values. Chemicals
(Merck/Schuchardt) were used as purchased. Literature methods
were applied in the preparation of [CoCl(PMe3)3],[14] [CoMe-
(PMe3)4],[15] [CoMe2(PMe3)3],[10] [CoClMe2(PMe3)3],[16] 2-(di-
phenylphosphanyl)aniline,[17] 2-(diphenylphosphanyl)-N-methylan-
Figure 5. Molecular structure of 13 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪN1
1.858(6), CoϪP1 2.212(2), P1ϪC1 1.798(8), C1ϪC2 1.398(10), iline,[18] and 2-(diphenylphosphanyl)-N,N-dimethylaniline.[19] IR:
C2ϪN1 1.389(9); C2ϪN1ϪCo 124.6(5), N1ϪC2ϪC1 117.0(7),
C2ϪC1ϪP1 111.5(6), C1ϪP1ϪCo 100.8(3)
Nujol mulls between KBr discs, Bruker spectrophotometer type
FRA 106. 1H and 13C NMR spectra (300 MHz and 75 MHz, re-
spectively) were recorded with a Bruker ARX-300 spectrometer, 31
P
NMR spectra (81 MHz) with a Bruker AM-200 instrument. 13C
and 31P NMR resonances were obtained with broad-band proton
decoupling. MS: Varian Mat-311 (FD). Magnetic susceptibility
data were obtained by the Faraday method, Cahn D 200 torsion
octahedral complexes of a low-spin Co (d6) ion. Complex
15 tends to lose one of the methyl groups since after re-
peated recrystallisations black crystals of 12 were obtained.
Reactions involving methylcobalt compounds thus far balance and Bruker BMN-200/60 magnet system at 1.5 Tesla.
have been directed towards a prechelate NH function and
proceed with the elimination of methane. Surprisingly,
[CoMe(PMe3)4] was found to react smoothly at Ϫ70 °C
with 2-(diphenylphosphanyl)-N,N-dimethylaniline. Evolu-
[2-(Diphenylphosphanyl)anilido-N,P]tris(trimethylphosphane)cobalt
(1). Method a: 2-(Diphenylphosphanyl)aniline (1202 mg,
3.70 mmol) in diethyl ether (40 mL) was combined with [CoM-
e(PMe3)4] (1400 mg, 3.70 mmol) in diethyl ether (40 mL) at Ϫ70
tion of gas was observed while heating to 20 °C, and even- °C causing the evolution of gas and giving a brown heterogeneous
mixture. This was heated to 20 °C and stirred for 1 h. The dark
solid of 1 was isolated by decanting and washing with cold pentane
and dried in vacuo. From the liquor, at 4 °C, another 260 mg of
black crystals of 1 were obtained. Combined yield 1710 mg (82%).
Method b: Chloro[2-(diphenylphosphanyl)anilido-N,P]bis(trime-
thylphosphane)cobalt (4) (980 mg, 1.87 mmol) and trimethylphos-
phane (1500 mg, 19.7 mmol) in THF (40 mL) were combined at
Ϫ70 °C with MeLi (1.6 ⁾ in diethyl ether (1.2 mL, 1.80 mmol)
causing the dark green colour to turn red brown. The mixture was
heated to 20 °C and stirred for 30 min. The volatiles were removed
in vacuo and the residue was extracted with three portions of di-
ethyl ether (80 mL). Fractional crystallisation at 4 °C afforded
black crystals of 1. Yield 664 mg (63%); m.p. 118Ϫ119 °C (dec.).
IR (Nujol): ν˜ ϭ 3331 cmϪ1 (NϪH). 1H NMR (300 MHz, [D8]THF,
233 K): δ ϭ 0.88 (br. s, 9 H, PCH3), 1.28 (br. s, 18 H, PCH3), 2.95
tually dark red crystals of 19 were obtained and found to
arise from a cyclometallation reaction [Equation (10)].
(10)
The 31P NMR spectrum at 233 K clearly shows the char-
acteristic shifts and coupling pattern of an ortho-metallated
tris(trimethylphosphane)cobalt complex.[12] As no further
signals are detected, the absence of possible isomers of 19
is confirmed. This unusual result is supported by the 13C
NMR spectroscopic data. Only ten resonances of aromatic
carbon nuclei were detected whereas eighteen are expected
to arise from altogether five available ortho-CH groups.
Consequently, a thorough search for isomers of 19 was
undertaken. In view of an 80% yield the synthesis was re-
peated on a larger scale (see Exp. Sect.) to afford 85% of
the product, and 270 mg of solid residue could be scrut-
3
3
(s, 1 H, NH), 5.69 (t, J ϭ 6.8 Hz, 1 H, CH), 6.23 (t, J ϭ 4.9 Hz,
3
3
1 H, CH), 6.38 (t, J ϭ 7.1 Hz, 1 H, CH), 7.06 (t, J ϭ 7.4 Hz, 1
H, CH), 7.19Ϫ7.25 (m, 6 H, CH), 7.62Ϫ7.66 (m, 4 H, CH) ppm.
31P NMR (81 MHz, [D8]THF, 233 K): δ ϭ Ϫ7 (dd, 2JP,P ϭ 99 and
2
61 Hz, 2 P, PCH3), 28 (dt, JP,P ϭ 61 and 60 Hz, 1 P, PC6H5), 52
(dt, 2JP,P ϭ 99 and 61 Hz, 1 P, PCH3) ppm. C27H42CoNP4 (563.5):
calcd. C 57.55, H 7.51, N 2.49, P 21.99; found C 58.29, H 7.53, N
2.48, P 21.60.
[2-(Diphenylphosphanyl)-N-methylanilido-N,P]tris(trimethyl-
inised by IR and 13C NMR spectroscopy. Again only the phosphane)cobalt (2). Method a: 2-(Diphenylphosphanyl)-N-
244
Eur. J. Inorg. Chem. 2003, 240Ϫ248

(Trimethylphosphane)cobalt Complexes Containing Chelating (2-Diphenylphosphanyl)anilido Ligands
FULL PAPER
3
methylaniline (750 mg, 1.95 mmol) in THF (50 mL) was combined
PCH3), 1.35 (br. s, 1 H, NH), 5.93 (dd, J ϭ 7.2, 4J ϭ 1.1 Hz, 1
4
with CoMe(PMe3)4 (740 mg, 1.95 mmol) in THF (50 mL) at 20 °C. H, CH), 6.34 (dd, 3J ϭ 5.1, JP,H ϭ 3.1 Hz, 1 H, CH), 6.60 (dd,
4
3
4
The mixture was stirred for 16 h and the solvents were evaporated 3J ϭ 6.7, J ϭ 1.4 Hz, 1 H, CH), 7.06 (dt, J ϭ 7.8, J ϭ 1.4 Hz,
to dryness in vacuo. The residue was extracted with two portions
of pentane (50 mL) and the red brown solution cooled to Ϫ27 °C
to afford a black solid which was isolated by decanting and drying
1 H, CH), 7.25Ϫ7.31 (m, 6 H, CH), 7.52Ϫ7.61 (m, 4 H, CH) ppm.
13C NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 18.6 (s, PCH3), 109.7
3
1
(d, JP,C ϭ 4.5 Hz, CH), 116.7 (d, JP,C ϭ 13.2 Hz, CH), 128.5 (d,
in vacuo to give a waxy solid of 2. Yield 395 mg (35%). Method b: 2JP,C ϭ 9.4 Hz, CH), 130.3 (s, CH), 132.7 (d, 2JP,C ϭ 12.5 Hz, CH),
Chloro[2-(diphenylphosphanyl)-N-methylaniline]bis(trimethyl-
phosphane)cobalt (5) (580 mg, 1.08 mmol) and trimethylphos-
133.8 (s, CH), 135.0, 142.0 (s, C) ppm. 31P NMR (81 MHz,
[D8]THF, 233 K): δ ϭ 5 (d, 2JP,P ϭ 97 Hz, 2 P, PCH3), 63 (t, 2JP,P ϭ
phane (1100 mg, 14.4 mmol) in THF (70 mL) were combined at 97 Hz, 1 P, PC6H5) ppm. C25H33CoNOP3 (515.4): calcd. C 58.26,
Ϫ70 °C with MeLi (1.6 ⁾ in diethyl ether (0.67 mL, 1.08 mmol) H 6.45, N 2.72, P 18.03; found C 58.03, H 6.64, N 2.66, P 18.11.
causing the dark green colour to turn red brown. The mixture was
Carbonyl[2-(diphenylphosphanyl)-N-methylanilido-N,P]bis(tri-
methylphosphane)cobalt (7): A sample of 2 (590 mg, 1.02 mmol) in
THF (70 mL) was stirred under 1 bar of CO for 30 min to afford
a light red solution. The volatiles were removed in vacuo and the
warmed to 20 °C and stirred for 30 min. The volatiles were removed
in vacuo and the residue was extracted with three 50 mL portions
of pentane. Crystallisation at 4 °C afforded black crystals of 2.
Yield 395 mg (29%); m.p. 130Ϫ135 °C (dec.). 1H NMR (300 MHz,
residue was extracted with two portions of pentane (70 mL). At 4
[D8]THF, 233 K): δ ϭ 0.90 (br. s, 9 H, PCH3), 1.25 (br. s, 18 H,
°C short dark red rods of 7 were obtained. Yield 492 mg (91%);
m.p. 165Ϫ170 °C (dec.). IR (Nujol): ν˜ ϭ 1906 cmϪ1 (CO). 1H
NMR (300 MHz, [D8]THF, 296 K): δ ϭ 1.17 (s, 18 H, PCH3), 2.74
PCH3), 2.66 (s, 3 H, NCH3), 5.80Ϫ7.78 (m, 14 H, CH) ppm. 31P
2
NMR (81 MHz, [D8]THF, 233 K): δ ϭ Ϫ8 (dd, JP,P ϭ 103 and
2
59 Hz, 2 P, PCH3), 29 (dt, JP,P ϭ 60 and 59 Hz, 1 P, PC6H5), 52
3
4
(s, 3 H, NCH3), 5.72 (dd, J ϭ 7.4, J ϭ 1.3 Hz, 1 H, CH), 6.22
(dt, 2JP,P ϭ 103 and 59 Hz, 1 P, PCH3) ppm. MS (70 eV): m/z (%) ϭ
577 (20) [Mϩ], 501 (30) [Mϩ Ϫ PMe3].
3
4
3
4
(dd, J ϭ 6.2, JP,H ϭ 2.8 Hz, 1 H, CH), 6.60 (dd, J ϭ 6.2, J ϭ
1.4 Hz, 1 H, CH), 7.15 (dd, 3J ϭ 7.4, 4J ϭ 1.4 Hz, 1 H, CH),
7.31Ϫ7.36 (m, 6 H, CH), 7.45Ϫ7.52 (m, 4 H, CH) ppm. 13C NMR
(75.4 MHz, [D8]THF, 296 K): δ ϭ 18.1 (s, PCH3), 39.4 (s, NCH3),
[2-(Diphenylphosphanyl)-N-methylanilido-N,P]bis(trimethylphos-
phane)cobalt
(3):
2-(Diphenylphosphanyl)aniline
(685 mg,
4
1
109.2 (s, CH), 112.5 (d, JP,C ϭ 4.9 Hz, CH), 117.2 (d, JP,C
ϭ
2.35 mmol) in THF (50 mL) was combined with [CoMe(PMe3)4]
(890 mg, 2.35 mmol) in THF (50 mL), at Ϫ70 °C, and after heating
to 20 °C, the mixture was stirred for 16 h. The volatiles were re-
moved in vacuo and the residue was extracted with two portions
of pentane (50 mL). Crystallisation at 4 °C afforded red brown rods
of 3. Yield 763 mg (69%); m.p. 135Ϫ136 °C (dec.). Magnetic mo-
ment (299 K): µeff ϭ 2.97 µB. C25H35CoNP3 (501.4): calcd. C 59.89,
H 7.04, N 2.79, P 18.53; found C 59.78, H 7.00, N 2.83, P 18.75.
14.9 Hz, CH), 127.4 (d, 2JP,C ϭ 12.3 Hz, CH), 130.3 (s, CH), 133.4
2
2
(d, JP,C ϭ 12.5 Hz, CH), 133.7, 135.0 (s, C), 169.1 (d, JP,C
ϭ
30.5 Hz, NC) ppm. 31P NMR (81 MHz, [D8]THF, 233 K): δ ϭ 6
2
2
(d, JP,P ϭ 97 Hz, 2 P, PCH3), 65 (t, JP,P ϭ 97 Hz, 1 P, PC6H5)
ppm. C26H35CoNOP3 (529.4): calcd. C 58.99, H 6.66, N 2.65, P
17.55; found C 58.98, H 6.73, N 2.55, P 17.48.
[2-(Diphenylphosphanyl)anilido-N,P](ethene)bis(trimethylphos-
phane)cobalt (8): A sample of 1 (580 mg, 1.02 mmol), suspended in
pentane (70 mL), was stirred under 1 bar of C2H4 for 30 min to
afford a red solution which was filtered and cooled to Ϫ27 °C.
Short red rods of 8 were dried in a stream of ethene at 20 °C. Yield
281 mg (53%); m.p. 45Ϫ50 °C (dec.). IR (Nujol): ν˜ ϭ 3342 cmϪ1
(NϪH). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 1.17 (d,
Chloro[2-(diphenylphosphanyl)aniline]bis(trimethylphosphane)cobalt
(4): 2-(Diphenylphosphanyl)aniline (584 mg, 2.10 mmol) in THF
(50 mL) was combined with CoCl(PMe3)3 (680 mg, 2.10 mmol) in
THF (50 mL) and within 10 min a dark green solution formed.
After 1 h, the volatiles were removed in vacuo and the residue was
extracted with three portions of diethyl ether (80 mL). Crystallis-
ation at 4 °C afforded dark green prisms of 4. Yield 716 mg (65%);
m.p. 126Ϫ127 °C (dec.). Magnetic moment (299 K): µeff ϭ 3.25 µB.
IR (Nujol): ν˜ ϭ 3404, 3211 cmϪ1 (NϪH). C24H34ClCoNP3 (523.8):
calcd. C 55.03, H 6.54, N 2.67, P 17.74; found C 55.09, H 6.40, N
2.66, P 17.89.
2
2JP,H ϭ 7.3 Hz, 9 H, PCH3), 1.32 (d, JP,H ϭ 4.5 Hz, 9 H, PCH3),
1.74 (m, 2 H, CϭCH2), 2.85 (m, 2 H, CϭCH2), 4.21 (br. s, 1 H,
NH), 5.85 (m, 1 H, CH), 5.94 (m, 1 H, CH), 6.71 (m, 2 H, CH),
7.35Ϫ7.39 (m, 6 H, CH), 7.75Ϫ7.78 (m, 4 H, CH) ppm. 13C NMR
(75.4 MHz, [D8]THF, 296 K): δ ϭ 17.8 (d, 1JP,C ϭ 19.4 Hz, PCH3),
20.4 (d, 1JP,C ϭ 16.3 Hz, PCH3), 44.1 (m, CH2), 108.1, 111.5, 123.2
(s, CH), 127.3 (m, C), 128.8, 130.7, 133.2 (s, CH), 134.4 (d, 2JP,C ϭ
25.3 Hz, C), 141.7 (s, CH) ppm. 31P NMR (81 MHz, [D8]THF,
193 K): δ ϭ 3 (dd, 2JP,P ϭ 34 and 52 Hz, 1 P, PCH3), 24 (dd, 2JP,P ϭ
Chloro[2-(diphenylphosphanyl)-N-methylaniline]bis(trimethyl-
phosphane)cobalt (5): 2-(Diphenylphosphanyl)-N-methylaniline
(803 mg, 2.75 mmol) in THF (50 mL) and [CoCl(PMe3)3] (890 mg,
2.75 mmol) in THF (50 mL) formed a dark green solution. After
1 h, the volatiles were removed in vacuo and the residue was ex-
tracted as above. Crystallisation at 4 °C afforded dark green plate-
lets of 5. Yield 1130 mg (77%); m.p. 130Ϫ131 °C (dec.). Magnetic
moment (299 K): µeff ϭ 3.29 µB. IR (Nujol): ν˜ ϭ 3332 cmϪ1
(NϪH). C25H36ClCoNP3 (537.9): calcd. C 55.83, H 6.75, N 2.60,
P 17.28; found C 55.78, H 6.52, N 2.58, P 17.33.
2
30 and 52 Hz, 1 P, PCH3), 61 (dd, JP,P ϭ 34 and 30 Hz, 1 P,
PC6H5) ppm. C26H37CoNP3 (515.4): calcd. C 60.59, H 7.24, N
2.72, P 18.03; found C 60.54, H 7.43, N 2.74, P 17.92.
[2-(Diphenylphosphanyl)-N-methylanilido-N,P](ethene)bis(trimethyl-
phosphane)cobalt (9): A sample of 2 (720 mg, 1.24 mmol) in pent-
ane (70 mL) was stirred under 1 bar of C2H4 for 30 min to afford
a red solution which was filtered and cooled to 4 °C. Short red
Carbonyl[2-(diphenylphosphanyl)anilido-N,P]bis(trimethylphos- rods of 9 were dried in a stream of ethene at 20 °C. Yield 410 mg
phane)cobalt (6): A sample of 1 (710 mg, 1.26 mmol) in THF (62%); m.p. 45Ϫ50 °C (dec.). 1H NMR (300 MHz, [D8]THF,
2
2
(70 mL) was stirred under 1 bar of CO for 30 min and afforded a
red solution. The volatiles were removed in vacuo and the residue
was extracted with two portions of pentane (70 mL). At 4 °C short
orange red rods of 6 were obtained. Yield 487 mg (75%); m.p.
296 K): δ ϭ 0.72 (d, JP,H ϭ 7.2 Hz, 9 H, PCH3), 1.30 (d, JP,H ϭ
3.9 Hz, 9 H, PCH3), 1.73 (m, 2 H, CϭCH2), 2.16 (s, 3 H, NCH3),
2.81 (m, 2 H, CϭCH2), 5.80 (m, 2 H, CH), 6.66Ϫ6.68 (m, 2 H,
CH), 7.31Ϫ7.33 (m, 6 H, CH), 7.67Ϫ7.75 (m, 4 H, CH) ppm. 13C
153Ϫ157 °C (dec.). IR (Nujol): ν˜ ϭ 3375 cmϪ1 (NϪH), 1887 cmϪ1 NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 17.8 (d, JP,C ϭ 22.6 Hz,
1
(CO). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 1.15 (s, 18 H, PCH3), 20.4 (d, JP,C ϭ 14.6 Hz, PCH3), 38.2 (s, NCH3), 45.3 (d,
1
Eur. J. Inorg. Chem. 2003, 240Ϫ248
245

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
2JP,C ϭ 18.3 Hz, CH2), 45.9 (m, CH2), 108.4, 111.0, 123.3 (s, CH),
two portions of diethyl ether (50 mL) and kept at 4 °C to afford
128.4 (d, 1JP,C ϭ 19.1 Hz, C), 128.8, 130.7, 133.2 (s, CH), 133.8 (d, crystals of 13. Yield 1150 mg (51%); decomp. Ͼ 250 °C. IR (Nujol):
2JP,C ϭ 24.3 Hz, C), 141.7 (s, CH), 166.0 (s, NC) ppm. 31P NMR ν˜ ϭ 3337 cmϪ1 (NϪH). Magnetic moment (299 K): µeff ϭ 2.05 µB.
2
(81 MHz, [D8]THF, 193 K): δ ϭ 3 (dd, JP,P ϭ 36 and 56 Hz, 1 P,
C36H30CoN2P2 (611.5): calcd. C 70.71, H 4.95, N 4.58, P 10.13;
found C 71.09, H 5.33, N 4.39, P 10.46.
2
2
PCH3), 23 (dd, JP,P ϭ 32 and 56 Hz, 1 P, PCH3), 61 (dd, JP,P
ϭ
36 and 32 Hz, 1 P, PC6H5) ppm. C27H39CoNP3 (529.2): calcd. C
61.25, H 7.42, N 2.65, P 17.55; found C 61.18, H 7.52, N 2.51,
P 17.62.
Bis[2-(diphenylphosphanyl)-N-methylanilido-N,P]cobalt
(14).
Method a: 2-(Diphenylphosphanyl)-N-methylaniline (1040 mg,
3.59 mmol) in diethyl ether (40 mL) and CoMe2(PMe3)3 (570 mg,
1.79 mmol) in diethyl ether (70 mL) were combined at Ϫ70 °C and
heated to 20 °C. After 5 h, the volatiles were removed in vacuo, the
solid residue was extracted with two portions of diethyl ether
(70 mL). Crystallisation at 4 °C afforded dark red crystals of
14.Yield 551 mg (48%). Method b: 2-(Diphenylphosphanyl)aniline
(1130 mg, 3.86 mmol) in THF (30 mL) and CoCl2 (250 mg,
1.93 mmol) in THF (70 mL) were combined at Ϫ70 °C and MeLi
(1.6 ) in diethyl ether (2.42 mL, 3.86 mmol) was added causing
the colour to turn dark red. The mixture was heated to 20 °C and
the volatiles were removed in vacuo. The residue was extracted with
two portions of diethyl ether (50 mL) and kept at 4 °C to afford
crystals of 14. Yield 390 mg (32%); decomp. Ͼ 202 °C. Magnetic
moment (299 K): µeff ϭ 2.33 µB. C38H34CoN2P2 (639.6): calcd. C
71.36, H 5.36, N 4.38, P 9.69; found C 70.78, H 5.46, N 4.39,
P 9.88.
[2-(Diphenylphosphanyl)-N-methylanilido-N,P](propene)bis(tri-
methylphosphane)cobalt (10): A sample of 2 (830 mg, 1.43 mmol)
in pentane (70 mL) was stirred under 1 bar of C3H6 for 30 min to
afford a red solution which was filtered and cooled to Ϫ27 °C. Red
triangular platelets of 10 together with those of 2 were dried in a
stream of propene at 20 °C and separated mechanically. Yield
179 mg (23%); m.p. 85Ϫ87 °C (dec.). 1H NMR (300 MHz,
2
[D8]THF, 296 K): δ ϭ 0.74 (d, JP,H ϭ 8.0 Hz, 9 H, PCH3), 1.30
(d, 2JP,H ϭ 6.1 Hz, 9 H, PCH3), 1.36 (m, 3 H, CCH3), 2.42 (s, 3 H,
NCH3), 2.79 (m, 1 H, CϭCH), 2.81 (m, 2 H, CϭCH2), 6.55 (m, 1
H, CH), 6.61 (m, 1 H, CH), 6.55 (m, 2 H, CH), 7.21Ϫ7.35 (m, 6 H,
CH), 7.65Ϫ7.80 (m, 4 H, CH) ppm. 31P NMR (81 MHz, [D8]THF,
193 K): δ ϭ 3 (dd, 2JP,P ϭ 38 and 52 Hz, 1 P, PCH3), 22 (dd, 2JP,P ϭ
2
30 and 52 Hz, 1 P, PCH3), 61 (dd, JP,P ϭ 38 and 30 Hz, 1 P,
PC6H5) ppm. C28H41CoNP3 (543.2): calcd. C 61.88, H 7.60, N
2.58, P 17.10; found C 61.08, H 7.65, N 2.56, P 17.41.
Bis[2-(diphenylphosphanyl)anilido-N,P](trimethylphosphane)cobalt
(15): A sample of 13 (660 mg, 1.07 mmol) was recrystallised from
diethyl ether (40 mL) containing excess trimethylphosphane
(280 mg, 3.67 mmol) at 4 °C to afford bunches of red brown crys-
tals. Yield 248 mg 15 (47%); m.p. 148Ϫ150 °C (dec.). IR (Nujol):
ν˜ ϭ 3337 cmϪ1 (NϪH). Magnetic moment (299 K): µeff ϭ 2.10 µB.
C39H39CoN2P3 (687.6): calcd. C 68.12, H 5.72, N 4.07, P 13.51;
found C 68.10, H 5.85, N 4.02, P 13.61.
[2-(Diphenylphosphanyl)-N-methylanilido-N,P](iodo)bis(trimethyl-
phosphane)cobalt(diethyl ether) (11): A sample of 2 (780 mg,
1.35 mmol) in THF (50 mL) was combined with iodomethane
(441 mg, 3.10 mmol), at Ϫ70 °C, and the solution heated to 20 °C
to form a heterogeneous mixture. After 3 h, an off-white solid of
tetramethylphosphonium iodide (IR) was removed by filtration and
the dark brown solution concentrated to dryness in vacuo. Extrac-
tion with three portions of diethyl ether (80 mL) and crystallisation
at 4 °C afforded black cubic crystals of 11. Yield 426 mg (45%);
m.p. 85Ϫ86 °C (dec.). Magnetic moment (299 K): µeff ϭ 2.09 µB.
C29H45CoINOP3 (702.4): calcd. C 49.59, H 6.46, N 1.99, P 13.23;
found C 50.20, H 6.12, N 2.10, P 14.03.
Bis[2-(diphenylphosphanyl)-N-methylanilido-N,P](trimethyl-
phosphane)cobalt (16): A sample of 14 (450 mg, 0.70 mmol) was
recrystallised from diethyl ether (50 mL) containing excess trime-
thylphosphane (730 mg, 9.59 mmol) at Ϫ27 °C to afford bunches
of short red brown rods of 16. Yield 206 mg (41%); m.p. 165Ϫ167
°C (dec.). Magnetic moment (299 K): µeff
C41H43CoN2P3 (715.7): calcd. C 68.81, H 6.06, N 3.91, P 12.98;
found C 68.79, H 5.45, N 4.06, P 13.25.
ϭ
2.04 µB.
[2-(Diphenylphosphanyl)anilido-N,P](methyl)bis(trimethylphos-
phane)cobalt (12): 2-(Diphenylphosphanyl)aniline (615 mg,
2.11 mmol) in diethyl ether (50 mL) and CoMe2(PMe3)3 (670 mg,
2.11 mmol) in diethyl ether (50 mL) were combined at Ϫ70 °C and
heated to 20 °C. After 16 h, the volatiles were removed in vacuo,
and the solid residue was extracted with two portions of pentane
(50 mL). Crystallisation at 4 °C afforded black crystals of 12. Yield
752 mg (71%); m.p. 117Ϫ119 °C (dec.). IR (Nujol): ν˜ ϭ 3341 cmϪ1
(NϪH). Magnetic moment (299 K): µeff ϭ 1.65 µB. MS (70 eV):
m/z (%) ϭ 502 (14) [Mϩ], 350 (30) [Mϩ Ϫ 2 PMe3]. C25H36CoNP3
(502.4): calcd. C 59.77, H 7.22, N 2.79, P 18.49; found C 59.78, H
7.12, N 2.78, P 18.31.
mer-trans-Dimethyl[2-(diphenylphosphanyl)anilido-N,P]bis(tri-
methylphosphane)cobalt
(17):
2-(Diphenylphosphanyl)aniline
(850 mg, 3.06 mmol) in diethyl ether (70 mL) were treated with
MeLi (1.6 ) in diethyl ether (1.9 mL, 3.06 mmol). At Ϫ70 °C,
CoClMe2(PMe3)3 (1080 mg, 3.06 mmol) in diethyl ether (50 mL)
was added to the mixture which was heated to 20 °C and stirred
for 16 h. The volatiles were removed in vacuo, and the solid residue
was extracted with two portions of pentane (70 mL). Crystallis-
ation at Ϫ27 °C afforded short orange rods of 17. Yield 1030 mg
(65%); m.p. 85Ϫ87 °C (dec.). IR (Nujol): ν˜ ϭ 3338 cmϪ1 (NϪH).
Bis[2-(diphenylphosphanyl)anilido-N,P]cobalt (13). Method a: 2-(Di-
phenylphosphanyl)aniline (1060 mg, 3.84 mmol) in diethyl ether
(50 mL) and CoMe2(PMe3)3 (610 mg, 1.92 mmol) in diethyl ether
(50 mL) were combined at Ϫ70 °C and heated to 20 °C. After 16 h,
the volatiles were removed in vacuo, the solid residue was washed
with cold pentane (5 mL) and extracted with two portions of di-
ethyl ether (50 mL). Crystallisation at 4 °C afforded dark red crys-
tals of 13. Yield 458 mg (39%). Method b: 2-(Diphenylphosphanyl)-
aniline (2050 mg, 7.39 mmol) in THF (30 mL) and CoCl2 (480 mg,
3.69 mmol) in THF (50 mL) were combined at Ϫ70 °C and MeLi
(1.6 ) in diethyl ether (4.6 mL, 7.39 mmol) was added causing the
colour to turn dark red. The mixture was warmed to 20 °C and
the volatiles were removed in vacuo. The residue was extracted with
1H NMR (200 MHz, [D8]THF, 233 K): δ ϭ Ϫ0.65 (q, JP,H
ϭ
3
3
6.6 Hz, 3 H, CoCH3), 0.50 (t, JP,H ϭ 9.9 Hz, 3 H, CoCH3), 0.67
3
(br. s, 18 H, PCH3), 1.47 (br. s, 1 H, NH), 6.02 (t, J ϭ 6.9 Hz, 1
3
3
H, CH), 6.37 (t, J ϭ 5.9 Hz, 1 H, CH), 6.67 (t, J ϭ 7.5 Hz, 1 H,
CH), 7.19Ϫ7.26 (m, 6 H, CH), 7.49 (m, 1 H, CH). 7.78Ϫ7.82 (m,
4 H, CH) ppm. 31P NMR (81 MHz, [D8]THF, 193 K): δ ϭ 12 (br.
s, 2 P, PCH3), 41 (br. s, 1 P, PC6H5) ppm. C26H39CoNP3 (517.5):
calcd. C 60.35, H 7.60, N 2.71, P 17.96; found C 60.09, H 7.60, N
2.65, P 17.99.
mer-trans-[2-(Diphenylphosphanyl)-N-methylanilido-N,P]dimethyl-
bis(trimethylphosphane)cobalt (18): 2-(Diphenylphosphanyl)-N-
methylaniline (345 mg, 1.18 mmol) in diethyl ether (70 mL) was
246
Eur. J. Inorg. Chem. 2003, 240Ϫ248

(Trimethylphosphane)cobalt Complexes Containing Chelating (2-Diphenylphosphanyl)anilido Ligands
treated with MeLi (1.6 ⁾ in diethyl ether (0.74 mL, 1.18 mmol). CB2 1EZ, UK [Fax: (internat.)
FULL PAPER
44-1223/336-033; E-mail:
ϩ
At Ϫ70 °C, CoClMe2(PMe3)3 (417 mg, 1.18 mmol) in diethyl ether deposit@ccdc.cam.ac.uk].
(50 mL) was added to the mixture which was heated to 20 °C and
stirred for 16 h. The volatiles were removed in vacuo, and the solid
residue was extracted with two portions of pentane (70 mL). Crys-
tallisation at Ϫ27 °C afforded short orange rods of 18. Yield
630 mg (59%); m.p. 89Ϫ91 °C (dec.). 1H NMR (300 MHz,
Table 2. Crystal data for compounds 3 and 6
3
6
[D8]THF, 233 K): δ ϭ Ϫ0.60 (q, 3JP,H ϭ 6.7 Hz, 3 H, CoCH3), 0.53 Empirical formula
C25H35CoNP3
501.4
0.44 ϫ 0.40 ϫ 0.36 0.44 ϫ 0.30 ϫ 0.26
monoclinic
P21/c
9.385(3)
12.502(2)
23.190(4)
92.66(2)
2718.0(11)
4
1.225
0.820
C25H33CoNOP3
515.4
3
Formula mass
Crystal size [mm]
Crystal system
Space group
(t, JP,H ϭ 9.2 Hz, 3 H, CoCH3), 0.64 (br. s, 18 H, PCH3), 2.48 (s,
3
3
3 H, NCH3), 6.20 (t, J ϭ 6.8 Hz, 1 H, CH), 6.35 (t, J ϭ 7.0 Hz,
monoclinic
P21
1 H, CH), 6.67 (t, 3J ϭ 7.9 Hz, 1 H, CH), 6.96Ϫ7.01 (m, 6 H, CH),
7.55 (t, J ϭ 6.8 Hz, 1 H, CH), 7.69Ϫ7.75 (m, 4 H, CH) ppm. 31P
3
˚
a [A]
9.8330(5)
15.1030(7)
18.1480(8)
89.940(4)
2695.1(2)
2
1.270
0.386
293(2)
4.8 Յ 2Θ Յ 48
Ϫ11 Յ h Յ 11
0 Յ k Յ 17
0 Յ l Յ 20
8138
2
NMR (81 MHz, [D8]THF, 193 K): δ ϭ 15 [d(br), JP,P ϭ 35 Hz, 2
P, PCH3), 40 (t, JP,P ϭ 35 Hz, 1 P, PC6H5) ppm. C27H41CoNP3
˚
b [A]
2
˚
c [A]
(531.5): calcd. C 61.02, H 7.78, N 2.64, P 17.48; found C 61.08, H
7.43, N 2.64, P 17.43.
β [°]
3
˚
V [A ]
Z
[3-(Dimethylamino)-2-(diphenylphosphanyl)phenyl-C1,P]tris(tri-
methylphosphane)cobalt (19): 2-(Diphenylphosphanyl)-N,N-di-
methylaniline (1100 mg, 3.60 mmol) in diethyl ether (50 mL) was
combined at Ϫ70 °C with CoMe(PMe3)4 (1360 mg, 3.60 mmol) in
diethyl ether (80 mL), with the evolution of a gas. The mixture was
heated to 20 °C and turned red brown. The volatiles were removed
in vacuo, the residue was extracted with two portions of pentane
(80 mL), and from the red solution dark red crystals of 19 were
Dcalcd. [g/cm3]
µ(Mo-Kα) [mmϪ1
]
Temperature [K]
293(2)
Data coll. range [°]
4.8 Յ 2Θ Յ 55
Ϫ1 Յ h Յ 12
Ϫ1 Յ k Յ 16
Ϫ30 Յ l Յ 30
h
k
l
No. reflect. measured 8023
No. unique data
Parameters
6232 (Rint ϭ 0.020) 4209 (Rint ϭ 0.0494)
278
1.008
0.0515
0.1171
1
obtained. Yield 1550 mg (85%); m.p. 112Ϫ113 °C (dec.). H NMR
544
(300 MHz, [D8]THF, 296 K): δ ϭ 1.02 (d, 2J
ϭ 5.6 Hz, 9 H, GoF on F2
1.117
0.0607
0.1639
P,H
R1 [I Ն 2σ(I)]
wR2 (all data)
PCH3), 1.23 (br. s, 18 H, PCH3), 2.13 (s, 6 H, NCH3), 5.90 (m, 1
H, CH), 6.19Ϫ6.28 (m, 2 H, CH), 7.22Ϫ7.24 (m, 6 H, CH),
7.75Ϫ7.79 (m, 4 H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF,
296 K): δ ϭ 22.2Ϫ22.7 (m, PCH3), 23.3 (m, PCH3), 43.3 (s, NCH3),
3
109.3 (s, CH), 125.9 (d, JP,C ϭ 3.1 Hz, CH), 126.0 (s, CH), 126.3
Table 3. Crystal data for compounds 12 and 13
3
3
(d, JP,C ϭ 5.6 Hz, CH), 126.9 (s, CH), 133.2 (d, JP,C ϭ 7.6 Hz,
3
1
CH), 133.3 (d, JP,C ϭ 7.6 Hz, CH), 139.1 (d, JP,C ϭ 9.6 Hz, C),
171.3 (m, CoC) ppm. 31P NMR (81 MHz, [D8]THF, 233 K): δ ϭ
Ϫ24 (dt, 2JP,P ϭ 89 and 68 Hz, 1 P, PC6H5), Ϫ4 (dt, 2JP,P ϭ 89 and
12
13
Empirical formula
Formula mass
Crystal size [mm]
Crystal system
Space group
C36H30CoN2P2
502.4
0.46 ϫ 0.40 ϫ 0.37 0.49 ϫ 0.38 ϫ 0.31
monoclinic
P21/n
9.908(2)
20.075(4)
13.311(2)
94.36(1)
2639.9(8)
4
1.264
0.844
C28H42CoIO0.5P3
611.6
2
47 Hz, 2 P, PCH3), 22 (dt, JP,P ϭ 68 and 47 Hz, 1 P, PCH3) ppm.
C29H46CoNP4 (591.5): calcd. C 58.89, H 7.84, N 2.37, P 20.95;
found C 58.92, H 7.82, N 2.27, P 20.83.
monoclinic
P21/a
˚
Crystal Structure Analyses: Crystal data are presented in Tables 2
and 3. Data collection: Complex 3: A crystal was sealed under ar-
gon in a glass capillary and mounted on a Bruker AXS P4 dif-
fractometer. Reflections were measured (ω-scans) using graphite-
monochromated Mo-Kα radiation; Lp correction and absorption
correction based on ψ-scans were applied. The structure was solved
by direct and conventional Fourier methods. All non-hydrogen
atoms were treated anisotropically, hydrogen atoms were treated
with a riding model in idealised positions. Complex 6: A crystal
was sealed under argon in a glass capillary and mounted on a Stoe
Stadi-4 diffractometer. Intensities were collected (ω-scans) using
graphite-monochromated Mo-Kα radiation. No absorption correc-
tion was applied. The structure was solved as for 3. Complex 12:
Crystal mounting, data collection, structure solution and refine-
ment as for 3. Complex 13: A crystal was sealed under argon in
a glass capillary and mounted on a Stoe Stadi-4 diffractometer.
Reflections were collected (ω-scans) using graphite-monochrom-
ated Mo-Kα radiation. Absorption corrections based on ψ-scans
were applied. The structure was solved as for 3. Crystallographic
data (excluding structure factors) for the structures reported in this
paper have been deposited with the Cambridge Crystallographic
Data Centre. Copies of the data (CCDC-184429 for 3, -186376
for 6, -184430 for 12, -186377 for 13) can be obtained free
of charge on application to CCDC, 12 Union Road, Cambridge
a [A]
11.5617(10)
14.9016(17)
17.8507(18)
101.384(9)
3015.0(5)
4
1.347
0.649
293(2)
5.4 Յ 2Θ Յ 50
Ϫ13 Յ h Յ 13
0 Յ k Յ 17
0 Յ l Յ 21
5689
˚
b [A]
˚
c [A]
β [°]
3
˚
V [A ]
Z
Dcalcd. [g/cm3]
µ(Mo-Kα) [mmϪ1
]
Temperature [K]
293(2)
Data coll. range [°]
4.0 Յ 2Θ Յ 55
Ϫ12 Յ h Յ 1
Ϫ26 Յ k Յ 1
Ϫ17 Յ l Յ 17
h
k
l
No. reflect. measured 7476
No. unique data
Parameters
6052 (Rint ϭ 0.0200) 5267 (Rint ϭ 0.0593)
278
1.046
0.0403
0.0985
373
GoF on F2
1.131
0.0657
0.2085
R1 [I Ն 2σ(I)]
wR2 (all data)
Acknowledgments
Financial support of this work by Fonds der Chemischen Industrie
is gratefully acknowledged.
Eur. J. Inorg. Chem. 2003, 240Ϫ248
247

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
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