Five- and six-membered cobaltocycles with C,P-chelating ligands through regiospecific cyclometalation of mono(2-substituted) triphenylphosphane

Article abstract of DOI:10.1002/ejic.200390179

Cyclometalation in the aliphatic ring occurs in the reaction between [CoCH₃(PMe₃)₄] and 5-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthalene to give [{8-(diphenylphosphanyl)-1,2,3,4-tetrahydronaphthyl-(C¹,P)} tris(trimethylphosphane)cobalt] (1), containing a five-membered metallacycle as shown in the molecular structure. While 1-(diphenylphosphanyl)naphthalene reacts accordingly, affording [{8-(diphenylphosphanyl)naphthyl-(C¹,P)}tris(trimethylphos phane)cobalt] (2), 2-(diphenylphosphanyl)biphenyl yields ortho-metalated [{2-(diphenylphosphanyl)-3-phenylphenyl-(C¹,P)}tris (trimethylphosphane)cobalt] (3), containing a four-membered metallacycle. 1-(Diphenylphosphanyl)-8-methylnaphthalene is metalated in the aliphatic substituent to form [{[8-(diphenylphosphanyl)naphth-1-yl]methyl-(C,P)}tris (trimethylphosphane)cobalt] (4). The molecular structure shows a trigonal-bipyramidal configuration of the cobalt atom accommodating a six-membered metallacycle. 2-(Diphenylphosphanyl)styrene replaces two trimethylphosphane ligands to give [{2-(diphenylphosphanyl)styrene-(C,C-η²,P)/methyl-bis (trimethylphosphane)cobalt] (5), avoiding metalation. Replacement of equatorial trimethylphosphane in compounds 1-3 by ethene gives π-ethene complexes 6-8. In the molecular structure of 7 the C-C vector of the π-ethene ligand is arranged in the equatorial plane of a trigonal bipyramid. Under 1 bar of CO, compound 2 forms a monocarbonyl complex 9, in which an equatorial carbonyl ligand is found in the molecular structure. Iodomethane transforms 2 into pentacoordinate [{2-(diphenylphosphanyl)naphthyl-(C¹,P)/iodobis- (trimethylphosphane)cobalt] (10) with retention of the metallacycle. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200390179

FULL PAPER
Five- and Six-Membered Cobaltocycles with C,P-Chelating Ligands through
Regiospecific Cyclometalation of Mono(2-Substituted) Triphenylphosphane
Hans-Friedrich Klein,*[a] Robert Beck,[a] Ulrich Flörke,[b] and Hans-Jürgen Haupt[b]
Keywords: Chelates / Cobalt / Metalation / Metallacycles / Structure elucidation
Cyclometalation in the aliphatic ring occurs in the reaction
between [CoCH3(PMe3)4] and 5-(diphenylphosphanyl)-
1,2,3,4-tetrahydronaphthalene to give [{8-(diphenylphos-
phanyl)-1,2,3,4-tetrahydronaphthyl-(C1,P)}tris(trimethyl-
phosphane)cobalt] (1), containing a five-membered metal-
lacycle as shown in the molecular structure. While 1-(di-
phenylphosphanyl)naphthalene reacts accordingly, affording
[{8-(diphenylphosphanyl)naphthyl-(C1,P)}tris(trimethylphos-
phane)cobalt] (2), 2-(diphenylphosphanyl)biphenyl yields or-
commodating a six-membered metallacycle. 2-(Diphenyl-
phosphanyl)styrene replaces two trimethylphosphane ligands
to give [{2-(diphenylphosphanyl)styrene-(C,C-η2,P)}methyl-
bis(trimethylphosphane)cobalt] (5), avoiding metalation. Re-
placement of equatorial trimethylphosphane in compounds
1−3 by ethene gives π-ethene complexes 6−8. In the molecu-
lar structure of 7 the C−C vector of the π-ethene ligand is
arranged in the equatorial plane of a trigonal bipyramid. Un-
der 1 bar of CO, compound 2 forms a monocarbonyl complex
9, in which an equatorial carbonyl ligand is found in the mo-
lecular structure. Iodomethane transforms 2 into pentacoord-
inate [{2-(diphenylphosphanyl)naphthyl-(C1,P)}iodobis-
(trimethylphosphane)cobalt] (10) with retention of the metal-
lacycle.
tho-metalated
[{2-(diphenylphosphanyl)-3-phenylphenyl-
(C1,P)}tris(trimethylphosphane)cobalt] (3), containing a four-
membered metallacycle. 1-(Diphenylphosphanyl)-8-methyl-
naphthalene is metalated in the aliphatic substituent to form
[{[8-(diphenylphosphanyl)naphth-1-yl]methyl-(C,P)}tris(tri-
methylphosphane)cobalt] (4). The molecular structure shows
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
a trigonal-bipyramidal configuration of the cobalt atom ac- Germany, 2003
Introduction
Cyclometalation reactions with mono(2-substituted) tri-
phenylphosphanes and [CoCH3(PMe3)4] proceed with elim-
ination of methane, whereby the selective product forma-
tion is rendered irreversible.[1] The observed regiospecificity,
based on the orientation of CϪH bonds situated in the
vicinity of the metal atom, is sterically controlled by the
preferred substrate conformation. Four-membered co-
baltocycles have been found to originate from an ortho-met-
alation process, while in exceptional cases five-membered
rings arise from attack in the side chain, although on the
basis of CϪH and CϪCo bond energies the balance is be-
lieved to be less favorable for C(sp3)ϪH bonds.[2] With the
aim of selectively generating larger metallacycles we have
metalated some pre-chelate phosphane ligands capable of
forming five- and six-membered cobaltocycles (Scheme 1).
An optional ortho-metalation route, disregarding the ortho-
CH groups in the phenyl substituents, is also indicated for
all four pre-chelate systems under investigation.
[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
Scheme 1. Projection of cyclometalation reactions
1380  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0407Ϫ1380 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2003, 1380Ϫ1387

Five and Six-Membered Cobaltocycles with C,P-Chelating Ligands
FULL PAPER
The cobalt atom is centered in a trigonal bipyramid with
axial CH and PMe3 groups and a five-membered metallacy-
cle spanning C-axial and P-equatorial positions with a
C39ϪCoϪP1 bite angle of 81.18(17)°. The CoϪC bond is
Results and Discussion
The ArCH3 Ǟ ArCH2 Ǟ ArCH Line
Proximity of a CϪH bond to the metal atom and a per-
pendicular orientation are believed to be necessary pre-
requisites for a cyclometalation reaction to occur. The un-
usual switching of selectivities from side-chain attack (2-
methyl substituent) to ortho-metalation (2-ethyl substitu-
ent), which is steric in origin, prompted us to clarify the
cyclometalation process further by restricting the proximity
conformations. Rotational orientations of CϪH bonds will
be restricted in an aliphatic ring when 5-(diphenylphos-
phanyl)-1,2,3,4-tetrahydronaphthalene is chosen as a pre-
chelate reactant. Reaction with [CoCH3(PMe3)4] proceeds
below 20 °C [Equation (1)].
˚
unusually long [CoϪC39 ϭ 2.082(6) A], and while the ad-
jacent distance C(sp3)ϪC(sp3) is shortened [C39ϪC38 ϭ
1.422(8) A] the C(sp3)ϪC(sp2) distance is normal
˚
˚
[C39ϪC40 ϭ 1.487(8) A]. A multiplet arising from multiple
phosphorus coupling at δ ϭ 1.08 ppm (1 H) in the 1H
NMR spectrum at 296 K is attributable to the CoCH
group, and there is nothing remarkable in the remaining
cycloaliphatic proton signals (δ ϭ 2.20Ϫ2.63 ppm, 6 H). As
there are no unusual anisotropic properties of the carbon
atoms, and as split models for the atomic positions of C39
and C38 were found insufficient, the structural irregularity
in the cycloaliphatic ring is attributed to packing forces.
Incorporation of the CH2 group in a cyclohexenyl ring
switches the cyclometalation reaction from ortho-metalation
of a C(sp2)ϪH bond to side-chain attack at a C(sp3)ϪH
bond.
(1)
1-(Diphenylphosphanyl)naphthalene, providing two in-
plane ortho-C(sp2)ϪH bonds, reacts with [CoCH3(PMe3)4]
at Ϫ70 °C [Equation (2)] to afford 2 exclusively, isolated
in 85% yield. The 31P NMR chemical shifts and coupling
constants at 193 K are found in positions and of an order
expected for a five-membered cobaltocycle. The configura-
tion of 2 was confirmed by monosubstitution with carbon
monoxide to afford 9 (see below). Formation of a similar
metallacycle starting from iridium() chloride was reported
to require reflux conditions in 2-methoxyethanol.[3]
Red-brown crystals of 1, melting with decomposition
above 121 °C, were obtained from pentane. In the 31P NMR
spectrum, the observed coordination chemical shift of δ ഠ
80 ppm is only compatible with the PPh2 group (δ ϭ
64 ppm) as part of a five-membered cobaltocycle. This con-
figuration was confirmed in the molecular structure of 1
(Figure 1).
(2)
In order to address the matter of preference of six- or
four-membered cobaltocycles, 2-(diphenylphosphanyl)bi-
phenyl was treated with [CoCH3(PMe3)4] [Equation (3)].
(3)
After evolution of gas, the mixture became red-brown in
color and afforded 3 as a waxy solid, which was charac-
terized by spectroscopy but gave no satisfactory elemental
analysis. Evidence for the presence of a four-membered co-
baltocycle was substantiated by its π-ethene derivative 8
(see below).
Figure 1. Molecular structure of 1 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪC39
2.082(6), CoϪP1 2.1612(17), CoϪP2 2.2189(17), CoϪP3
2.1911(18), CoϪP4 2.223(2), P1ϪC31 1.837(6), C31ϪC40 1.401(8),
C39ϪC40 1.487(8); C39ϪCoϪP1 81.18(17), C39ϪCoϪP2
88.12(18), C39ϪCoϪP3 85.34(19), C39ϪCoϪP4 176.58(18),
P1ϪCoϪP2 120.50(7), P1ϪCoϪP3 117.05(7), P1ϪCoϪP4
95.56(6), P2ϪCoϪP3 120.11(7), P2ϪCoϪP4 94.45(7), P3ϪCoϪP4
95.29(7), CoϪP1ϪC31 105.26(19), P1ϪC31ϪC40 110.3(4),
C31ϪC40ϪC39 117.8(5), CoϪC39ϪC40 116.5(4)
Metalation of the congested methyl group in 1-(diphenyl-
phosphanyl)-8-methylnaphthalene should provide a six-
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387
1381

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
membered cobaltocycle, if not dominated by ortho-metal- only minor deviations from the molecular structure of 1
ation (Scheme 1). The relative proximity effects at the co- (Figure 1).
balt center upon coordination of the anchoring PPh2 group
allow reaction with [CoCH3(PMe3)4] at Ϫ70 °C and evol- (diphenylphosphanyl)styrene (Scheme 1). However, treat-
ution of methane to proceed within 5 min. ment with [CoCH3(PMe3)4] failed to show evolution of gas,
Formation of all three ring sizes can be envisaged in 2-
Metalation occurs specifically at the naphthylmethyl proceeding instead by substitution of two trimethylphos-
group, forming the six-membered metallacycle [Equa- phane ligands [Equation (5)].
tion (4)]. Compound 4 was crystallized from pentane as
short, dark brown rods. The 31P NMR spectrum shows two
doublets of triplets and a doublet of doublets, as in the five-
membered cobaltocycles of 1 or 2. The observed pattern is
in agreement with axial CH2 and PMe3 groups and three
(5)
P donor functions in equatorial positions. A six-membered
chelate ring spanning axial C and equatorial P sites of a
trigonal bipyramid is shown in the molecular structure of
4 (Figure 2).
Compound 5 was obtained as an orange solid, decom-
posing above 152 °C under argon and stable in air under
1
ambient conditions for at least 2 h. In the H NMR spec-
trum at 296 K, a doublet of triplets at δ ϭ Ϫ0.85 ppm (3
H) represents the CoCH3 group, while in the 31P NMR
spectrum at 233 K, two doublets of doublets for an axial
(4)
and two anisochronic equatorial P-donor atoms indicate a
tbp-coordinated cobalt atom with local Cs symmetry
caused by an equatorial π-vinyl ligand. 2-(Diphenylphos-
phanyl)styrene appears to be trapped as a neutral chelating
ligand[4] that does not undergo a metalation reaction.
Reactions with Ethene
π-Olefin coordination in aryl(trimethylphosphane)cob-
alt() complexes is usually achieved through a smooth sub-
stitution reaction.[1a,5] Complex 6 was observed to crys-
tallize much better under 1 bar of ethene than under argon.
The underlying replacement of dissociated trimeth-
ylphosphane by ethene [Equations (6) and (7)] converts 1
and 2 into π-ethene compounds that form orange plates (6)
and short orange rods (7) from pentane solutions.
(6)
Figure 2. Molecular structure of 4 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪC1
2.090 (3), CoϪP1 2.1438(9), CoϪP2 2.1904(12), CoϪP3
(7)
2.1932(10), CoϪP4 2.2180(11), P1ϪC10 1.859(3), C10ϪC11
1.421(4), C2ϪC11 1.420(4), C1ϪC2 1.484(4); C1ϪCoϪP1
79.72(9), C1ϪCoϪP2 176.61(10), C1ϪCoϪP3 88.32(10),
C1ϪCoϪP4 85.25(9), P1ϪCoϪP2 98.60(4), P1ϪCoϪP3 120.87(4),
P1ϪCoϪP4 121.21(4), P2ϪCoϪP3 95.06(4), P2ϪCoϪP4 93.18(4),
P3ϪCoϪP4 115.02(4), CoϪP1ϪC10 117.05(10), P1ϪC10ϪC11
120.4(2), C2ϪC11ϪC10 123.5(2), C11ϪC2ϪC1 121.7(3),
CoϪC1ϪC2 123.4(2)
When the complexes are heated under argon, decompo-
sition (6: Ͼ 101 °C; 7: Ͼ 105 °C) proceeds with release of
ethene, and no alteration in the five-membered metallacycle
was indicated (IR) prior to deposition of cobalt. The ex-
The cobalt atom is situated 109.5(1) pm above the best pected tbp configuration was confirmed in the molecular
plane in the chelate ring. Bond lengths and angles show structure of 7 (Figure 3).
1382
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387

Five and Six-Membered Cobaltocycles with C,P-Chelating Ligands
FULL PAPER
Three doublets of doublets in the 31P NMR spectrum of
8, at δ ϭ Ϫ11, 9, and 21 ppm, fall in the positions corre-
sponding to a four-membered cobaltocycle expected from
data for ortho-metalated compounds[1] and indicate an
equatorial position of the π-ethene ligand.
Reaction with Carbon Monoxide
In solution under 1 bar of CO at 20 °C, 2 forms a mono-
carbonyl complexe 9 [Equation (9)].
(9)
The dark red crystals of 9 are thermally about 30 K more
stable than their parent trimethylphosphane compound and
are less air-sensitive. 31P NMR spectra obtained from THF
solutions show a mixture of isomers with JP,P coupling con-
stants consistent with tbp configurations in which a ter-
minal carbonyl ligand resides either in an axial or in an
equatorial position. In toluene solution, only the isomer
with axial CO is observed.
The molecular structure of 9 (Figure 4) shows the tbp
configuration of the isomer containing an equatorial car-
bonyl ligand and, in view of the otherwise similar infrared
spectra, confirms the presence of a five-membered co-
baltocycle in 2. The chelate bite angle in 9 [C38ϪCoϪP1 ϭ
83.97(12)°] is as in 7, and the sum of internal angles (534.7°)
indicates little deviation from planarity. The CoϪCO dis-
Figure 3. Molecular structure of 7 (molecule A) (ORTEP plot with
˚
hydrogen atoms omitted); selected bond lengths [A] and angles [°]:
CoϪC109 2.001(5), CoϪC151 2.026(6), CoϪC152 2.045(7),
CoϪP11 2.1830(16), CoϪP12 2.2413(18), CoϪP13 2.2097(17),
P11ϪC101 1.821(6), C101ϪC110 1.409(7), C109ϪC110 1.432(7);
C109ϪCoϪP11
83.82(16),
C109ϪCoϪP12
174.07(16),
C109ϪCoϪP13 88.06(17), P11ϪCoϪP12 99.20(6), P11ϪCoϪP13
105.74(6), P12ϪCoϪP13 95.98(7), CoϪP11ϪC101 102.55(18),
P11ϪC101ϪC110
CoϪC109ϪC110 118.5(4)
111.0(4),
C101ϪC110ϪC109
119.0(5),
A cobalt atom is found in the central position of a trig-
onal bipyramid with axial C and PMe3 donor groups and
a side-on coordinated ethene ligand with its CϪC vector
arranged in the equatorial plane, although crowded by PPh2
and PMe3 groups. The chelate bite angle [C109ϪCoϪP ϭ
83.82(16)°] is only 2° larger than in 1, and the axial PϪCo
˚
distance [CoϪP12 ϭ 2.2413(18) A] is again the longest in
the molecule, due to the trans influence of the naphthyl li-
gand.
Irrespective of the ring size or the heteroatom in P,C-,
P,N-, and P,O-cobaltocycles, coordination of ethene in tbp
complex molecules is regioselective, due to a better overlap
with the strongest π-acceptor ligand in an equatorial posi-
tion.[6]
A smooth replacement of trimethylphosphane by ethene
also proceeds [Equation (8)] with complex 3, which contains
a four-membered cobaltocycle.
Figure 4. Molecular structure of 9 (ORTEP plot with hydrogen
˚
atoms omitted); selected bond lengths [A] and angles [°]: CoϪC38
1.996(4), CoϪC1 1.720(5), CoϪP1 2.1753(12), CoϪP2 2.1935(13),
CoϪP3 2.2213(13), P1ϪC30 1.824(4), C30ϪC39 1.410(6),
C38ϪC39 1.445(5); C38ϪCoϪP1 83.97(12), C38ϪCoϪP2
176.71(13), C38ϪCoϪP3 85.07(12), P1ϪCoϪP2 98.10(5),
P1ϪCoϪP3 113.16(5), P2ϪCoϪP3 96.41(5), CoϪP1ϪC30
103.09(14), P1ϪC30ϪC39 110.1(3), C30ϪC39ϪC38 119.6(4),
CoϪC38ϪC39 118.0(3)
(8)
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387
1383

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
˚
methylnaphthalene (4.20 g, 15.7 mmol) in 50 mL of diethyl ether,
and the mixture was allowed to warm to Ϫ30 °C. After 2 h, chloro-
diphenylphosphane (3.45 g, 15.7 mmol) was added, and the re-
sulting suspension was stirred at 20 °C for 4 h. The volatiles were
then removed in vacuo and the residue was extracted with two por-
tions of methylcyclohexane (each 50 mL). On cooling of the com-
bined extracts to 4 °C, white cubic crystals (1.89 g, 37%) were
tance [CoϪC1 ϭ 1.720(5) A] is at the short end of the range
for monocarbonylcobalt() complexes although in most
cases the CO ligand occupies an axial position.[7]
Reactions with Iodomethane
Iodomethane oxidizes 2 [Equation (10)] to form a co-
balt() complex 10 without there being evidence of a co-
balt() intermediate.[1a] Although the molecular geometry
of 10 has not been clarified, the magnetic moment of 1.91
is as would be expected for a tbp configuration at the cobalt
atom (d7).[1a,8]
1
formed; m.p. 131Ϫ132 °C. H NMR (300 MHz, CD2Cl2, 296 K):
δ ϭ 3.08 (d, JP,H ϭ 4.2 Hz, 3 H, CH3), 7.12 (ddd, 3J ϭ 6.5, 4JP,H ϭ
4
5.0, J ϭ 1.5 Hz, 1 H, CH), 7.21Ϫ7.28 (m, 6 H, CH), 7.31Ϫ7.32
3
(m, 1 H, CH), 7.34 Ϫ7.38 (m, 6 H, CH), 7.73 (d, J ϭ 7.9 Hz, 1
H, CH), 7.85 (dd, 3J ϭ 8.1, 4J ϭ 1.4 Hz, 1 H, CH) ppm. 13C NMR
1
(75.4 MHz, CD2Cl2, 296 K): δ ϭ 27.5 (d, JP,C ϭ 32.0 Hz, CH3),
2
125.2 (s, CH), 125.9 (s, CH), 126.6 (d, JP,C ϭ 16.3 Hz, C), 128.5
2
(s, CH), 129.2 (d, JP,C ϭ 16.5 Hz, CH), 131.3 (s, CH), 131.9 (s,
3
CH), 132.2 (m, CH), 134.6 (d, JP,C ϭ 20.4 Hz, CH), 135.5 (d,
3JP,C ϭ 29.3 Hz, C), 135.9 (s, CH), 136.0 (s, C), 136.7 (s, C), 139.1
(d, 2JP,C ϭ 14.0 Hz, C) ppm. 31P NMR (81 MHz, CD2Cl2, 296 K):
δ ϭ Ϫ0.5 ppm. C23H19P (326.2): calcd. C 84.64, H 5.87; found C
84.17, H 5.98.
(10)
[{8-(Diphenylphosphanyl)-1,2,3,4-tetrahydronaphthyl-(C1,P)}tris-
(trimethylphosphane)cobalt(I)] (1): 5-(Diphenylphosphanyl)-1,2,3,4-
tetrahydronaphthalene (685 mg, 2.16 mmol) in THF (50 mL) was
mixed at Ϫ70 °C with [CoCH3(PMe3)4] (820 mg, 2.16 mmol) in
THF (50 mL). On warming, the mixture turned red-brown and was
stirred at 20 °C for 16 h. The volatiles were then removed in vacuo,
and the waxy residue was extracted with pentane (two 50-mL por-
tions). At 4 °C, the solution afforded deep-red octahedral crystals
of 1, suitable for X-ray diffraction. Yield 535 mg (41%); m.p.
Conclusion
The irreversible cyclometalation processes with
[CoCH3(PMe3)4] appear to depend on the conformation of
the 2-substituent when accommodated within the first coor-
dination sphere of the metal atom. As soon as proximity to
the electron-rich metal center is optimized, the product is
formed by a sequence of fast steps involving oxidative ad-
dition of an aliphatic or an aromatic CH group, followed
by elimination of methane. The ring size of the C,P-co-
baltocycles in the product complex may be four, five, or six
and does not dictate the regiospecificity of the cyclometal-
ation reaction. Neither cobaltocycle inserts a π-coordinated
ethene ligand into the CoϪC bond and neither is expanded
by CO uptake as with four-membered cobaltocycles.[1]
1
121Ϫ123 °C. H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.98 (d,
2JP,H ϭ 6.3 Hz, 9 H, PCH3), 1.08 (m, 1 H, CoCH), 1.25 (m, 18 H,
2
PCH3), 2.20 (m, 2 H, CH2), 2.48 (m, 2 H, CH2), 2.63 (dd, JP,H
ϭ
8.2, 7.6 Hz, 2 H, CH2), 5.89 (m, 1 H, CH), 6.75Ϫ6.79 (m, 2 H,
CH), 7.09Ϫ7.12 (m, 6 H, CH), 7.52Ϫ7.55 (m, 4 H, CH) ppm. 13C
NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 21.7 (m, PCH3), 23.1 (m,
CoCH), 23.9 (m, CH2), 25.6 (m, CH2), 27.4 (m, CH2), 123.1(d,
3
3JP,C ϭ 4.3 Hz, CH), 125.4 (s, CH), 126.1 (d, JP,C ϭ 7.6 Hz, CH),
2
126.2 (s, CH), 126.5 (s, CH), 131.9 (d, JP,C ϭ 13.0 Hz, CH), 133.6
(s, C) ppm. 31P NMR (81 MHz, [D8]THF, 233 K): δ ϭ Ϫ3 (dd,
2JPeq,Peq ϭ 97, 2JPeq,Pax ϭ 53 Hz, 2 P, PCH3), 24 (dt, 2JPax,Peq ϭ 53,
2
2
2JPax,Peq ϭ 53 Hz, 1 P, PCH3), 64 (dt, JPeq,Peq ϭ 97, JPeq,Pax
ϭ
53 Hz, 1 P, PPh2) ppm. C31H47CoP4 (602.5): calcd. C 61.79, H 7.86,
P 20.56; found C 61.47, H 7.47, P 21.05.
Experimental Section
General Procedures and Materials: All air-sensitive and volatile ma-
terials were handled by use of standard vacuum techniques and
were kept under argon. Microanalyses: Kolbe Microanalytical Lab-
oratory, Mülheim/Ruhr, FRG. Melting points/decomposition tem-
peratures: sealed capillaries, uncorrected values. Chemicals (Merck/
Schuchardt) were used as purchased. Literature methods were ap-
plied in the preparation of 1-iodo-8-methylnaphthalene,[9] 5-(di-
phenylphosphanyl)-1,2,3,4-tetrahydronaphthalene,[10] 2-(diphenyl-
phosphanyl)biphenyl,[11] 2-(diphenylphosphanyl)stryrene,[12] and
[CoCH3(PMe3)4].[13] 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 with a Cahn D 200 torsion bal-
ance (Bruker) at 1.5 Tesla.
[{8-(Diphenylphosphanyl)naphthyl-(C1,P)}tris(trimethylphosphane)-
cobalt(I)] (2): 1-(Diphenylphosphanyl)naphthalene (710 mg,
2.27 mmol) in THF (50 mL) was mixed at Ϫ70 °C with
[CoCH3(PMe3)4] (860 mg, 2.27 mmol) in THF (50 mL). On warm-
ing, the mixture turned red-brown and was stirred at 20 °C for 16 h.
The volatiles were then removed in vacuo, and the waxy residue was
extracted with diethyl ether (three 80-mL portions). At Ϫ27 °C, the
solution afforded black rhombuses of 2. Yield 1150 mg (85%); m.p.
107Ϫ109 °C (dec.). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ
2
1.01 (d, JP,H ϭ 6.4 Hz, 9 H, PCH3), 1.09 (m, 18 H, PCH3), 6.88
3
(t, J ϭ 7.6 Hz, 1 H, CH), 7.12 (m, 2 H, CH), 7.19Ϫ7.21 (m, 2 H,
CH), 7.39Ϫ7.47 (m, 7 H, CH), 7.61Ϫ7.69 (m, 4 H, CH) ppm. 13C
1
NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 21.9 (dd, JP,C ϭ 14.2,
3JP,C ϭ 7.6 Hz, PCH3), 22.5 (m, PCH3), 117.6 (s, CH), 122.6 (s,
CH), 122.8 (d, 3JP,C ϭ 6.1 Hz, CH), 124.6 (s, CH), 126.2 (d, 3JP,C ϭ
1
7.6 Hz, CH), 126.4 (s, CH), 127.2 (s, CH), 131.6 (d, JP,C
ϭ
2
2
15.2 Hz, C), 132.2 (d, JP,C ϭ 12.2 Hz, CH), 139.8 (d, JP,C
ϭ
1-(Diphenylphosphanyl)-8-methylnaphthalene: nBuLi (9.7 mL 1.6 
in hexane, 15.7 mmol) was added slowly at Ϫ70 °C to 1-iodo-8-
12.2 Hz, C), 142.3 (m, C) ppm. 31P NMR (81 MHz, [D8]THF,
233 K): δ ϭ Ϫ3 (dd, 2JPeq,Peq ϭ 100, 2JPeq,Pax ϭ 54 Hz, 2 P, PCH3),
1384
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387

Five and Six-Membered Cobaltocycles with C,P-Chelating Ligands
FULL PAPER
2
2
3
24 (dt, JPax,Peq ϭ 54, JPax,Peq ϭ 54 Hz, 1 P, PCH3), 64 (dt, 126.7 (d, JP,C ϭ 7.7 Hz, CH), 127.3 (s, CH), 127.8 (s, CH), 130 (s,
2
2
2
2JPeq,Peq ϭ 100, JPeq,Pax ϭ 54 Hz, 1 P, PPh2) ppm. C31H43CoP4
CH), 132.8 (d, JP,C ϭ 10.5 Hz, C), 133.2 (d, JP,C ϭ 9.8 Hz, CH),
137.8 (s, C), 138.4 (s, C) ppm. 31P NMR (81 MHz, [D8]THF,
233 K): δ ϭ 9 (dd, 2JPeq,Pax ϭ 44, 2JPeq,Pax ϭ 26 Hz, 2 P, PCH3), 71
(dd, 2JPax,Peq ϭ 26, 2JPax,Peq ϭ 44 Hz, 1 P, PPh2) ppm. C27H38CoP3
(514.2): calcd. C 63.04, H 7.45, P 18.06; found C 63.44, H 6.79,
P 18.18.
(598.5): calcd. C 62.21, H 7.24, P 20.70; found C 61.43, H 7.36,
P 21.11.
[{2-(Diphenylphosphanyl)-3-phenylphenyl-(C1,P)}tris(trimethyl-
phosphane)cobalt(I)] (3): 2-(Diphenylphosphanyl)biphenyl (608 mg,
1.79 mmol) in THF (50 mL) was mixed at Ϫ70 °C with
[CoCH3(PMe3)4] (680 mg, 1.79 mmol) in THF (30 mL). After
warming, the dark red mixture was stirred at 20 °C for 5 h, and
the volatiles were then removed in vacuo. The solid residue was
extracted with pentane (80 mL). No crystallization was achieved
either at 4 or at Ϫ27 °C from pentane, diethyl ether, THF, or mix-
tures of these solvents. Evaporation of solvent afforded 3 as a dark-
red, waxy solid. Crude yield 940 mg. 1H NMR (300 MHz,
[{8-(Diphenylphosphanyl)-1,2,3,4-tetrahydronaphthyl-(C1,P)}-
(ethene)bis(trimethylphosphane)cobalt(I)] (6): A sample of 3
(620 mg, 1.03 mmol) in diethyl ether (30 mL) was stirred under 1
bar of ethene for 1 h to provide an orange-red solution. The vol-
atiles were removed in vacuo and the solid residue was extracted
with pentane (40 mL). Crystallization at 4 °C afforded orange, hex-
agonal plates of 6. Yield 490 mg (86%); m.p. 101Ϫ103 °C (dec.).
1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.98 (d, 2JP,H ϭ 6.3 Hz,
9 H, PCH3), 1.08 (m, 1 H, CoCH), 1.25 (br. s, 9 H, PCH3),
2
[D8]THF, 296 K): δ ϭ 1.05 (d, JP,H ϭ 6.4 Hz, 9 H, PCH3), 1.30
(tЈ, |2JP,H
ϩ
4JP,H| ϭ 4.6 Hz, 18 H, PCH3), 5.40Ϫ7.70 (m, 18 H,
CH) ppm. 31P NMR (81 MHz, [D8]THF, 233 K): δ ϭ Ϫ21 (dt,
3
2.19Ϫ2.21 (m, 2 H, CH2), 2.48 (m, 2 H, CH2), 2.63 (dd, J ϭ 8.2,
2JPeq,Peq ϭ 90, JPeq,Pax ϭ 71 Hz, 1 P, PPh2), Ϫ4 (dd, JPeq,Peq
ϭ
2
2
3J ϭ 7.6 Hz, 2 H, CH2), 5.89 (m, 1 H, CH), 6.75Ϫ6.79 (m, 2 H,
90, 2JPeq,Pax ϭ 48 Hz, 2 P, PCH3), 21 (dt, 2JPax,Peq ϭ 71, 2JPax,Peq ϭ
1
CH), 7.09Ϫ7.12 (m, 2 H, CH), 7.52Ϫ7.55 (m, 4 H, CH) ppm. H
48 Hz, 1 P, PCH3) ppm.
NMR (300 MHz, [D8]toluene, 296 K): δ ϭ 0.53 (d, 2JP,H ϭ 6.4 Hz,
2
9 H, PCH3), 0.86 (m, 1 H, CoCH), 1.05 (d, JP,H ϭ 5.0 Hz, 9 H,
[{[8-(Diphenylphosphanyl)naphth-1-yl]methyl-(C,P)}tris(trimethyl-
phosphane)cobalt(I)] (4): 1-(Diphenylphosphanyl)-8-methylnaph-
PCH3), 1.88Ϫ2.54 (m, 6 H, CH2), 1.90 (m, 2 H, ϭCH2), 2.29 (m,
2 H, ϭCH2), 5.35 (m, 1 H, CH), 6.42Ϫ6.59 (m, 2 H, CH),
6.92Ϫ7.03 (m, 2 H, CH), 7.61Ϫ7.84 (m, 4 H, CH) ppm. 13C NMR
(75.4 MHz, [D8]THF, 296 K): δ ϭ 16.3 (d, 1JP,C ϭ 19.5 Hz, PCH3),
thalene (740 mg, 2.26 mmol) in THF (50 mL) was added at Ϫ78
°C to a solution of [CoCH3(PMe3)4] (857 mg, 2.26 mmol) in THF
(50 mL). A rapid change of color from dark red to brown was
observed as the solution warmed up. After 5 h, the solvent was
removed in vacuo and the residue was extracted with pentane (two
portions of 50 mL). Crystallization at 4 °C afforded dark brown
cubes of 4, suitable for X-ray diffraction. Yield 625 mg (45%); m.p.
146Ϫ148 °C (dec.). 1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ
1
19.1 (d, JP,C ϭ 19.5 Hz, PCH3), 23.4 (m, CoCH), 25.4 (m, CH2),
27.6 (s, CH2), 29.1 (s, CH2), 39.2 (m, ϭCH2), 40.9 (m, ϭCH2),
3
121.1 (s, CH), 123.2 (d, JP,C ϭ 5.2 Hz, CH), 124.7 (s, CH), 126.1
2
1
(d, JP,C ϭ 12.3 Hz, C), 126.2 (d, JP,C ϭ 15.1 Hz, C), 126.9 (d,
2JP,C ϭ 12.7 Hz, CH), 127.2 (d, JP,C ϭ 20.5 Hz, CH), 131.8 (d,
1
1JP,C ϭ 16.3 Hz, C), 132. 4 (d, JP,C ϭ 11.8 Hz, CH), 140.2 (s, C)
2
3
1.02 (s, 27 H, PCH3), 1.92 (q, JP,H ϭ 11.7 Hz, 2 H, CoCH2), 6.72
ppm. 13C NMR (75.4 MHz, [D8]toluene, 296 K): δ ϭ 18.1 (d,
(dt, 3J ϭ 7.5, 4J ϭ 0.8 Hz, 1 H, CH), 7.03 (dt, 3J ϭ 7.8, 4J ϭ
2.5 Hz, 2 H, CH), 7.16Ϫ7.21 (m, 6 H, CH), 7.31Ϫ7.33 (m, 2 H,
CH), 7.42Ϫ7.47 (m, 4 H, CH), 7.67 (d, 3J ϭ 8.0 Hz, 1 H, CH)
ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 11.6 (m,
1JP,C ϭ 18.4 Hz, PCH3), 21.8 (d, JP,C ϭ 19.3 Hz, PCH3), 23.3 (m,
1
CoCH), 26.8 (m, CH2), 29.0 (s, CH2), 30.5 (s, CH2), 41.1 (d, 2JP,C ϭ
2
18.2 Hz, ϭCH2), 42.4 (d, JP,C ϭ 16.4 Hz, ϭCH2), 122.8 (s, CH),
124.7 (d, JP,C ϭ 14.2 Hz, CH), 124.8 (s, CH), 127.6 (d, JP,C
2
2
ϭ
3
CoCH2), 19.8 (m, PCH3), 122.0 (d, JP,C ϭ 4.3 Hz, CH), 125.4 (s,
3
11.2 Hz, CH), 128.4 (s, C), 133.2 (d, JP,C ϭ 10.5 Hz, CH), 133.5
3
CH), 126.1 (d, JP,C ϭ 7.6 Hz, CH), 126.2 (s, CH), 126.5 (s, CH),
3
2
(d, JP,C ϭ 9.5 Hz, CH), 134.4 (d, JP,C ϭ 16.1 Hz, C), 141.7 (d,
2
131.9 (d, JP,C ϭ 13.0 Hz, CH), 133.6 (s, C) ppm. 31P NMR
2JP,C ϭ 22.6 Hz, CH), 155.0 (d, 1JP,C ϭ 43.7 Hz, C) ppm. 31P NMR
2
(81 MHz, [D8]THF, 203 K):
δ
ϭ
Ϫ3 (dd, JPeq,Peq
ϭ
102,
ϭ
2
2
(81 MHz, [D8]THF, 213 K): δ ϭ 5 (dd, JPeq,Pax ϭ 46, JPeq,Peq
38 Hz, 1 P, PCH3), 17 (dd, JPax,Peq ϭ 32, JPax,Peq ϭ 46 Hz, 1 P,
PCH3), 75 (dd, JPeq,Pax ϭ 32, JPeq,Peq ϭ 38 Hz, 1 P, PPh2) ppm.
C30H42CoP3 (554.5): calcd. C 64.98, H 7.63, P 16.76; found C
65.36, H 7.82, P 16.39.
ϭ
2JPeq,Pax ϭ 40 Hz, 2 P, PCH3), 20 (dt, JPax,Peq ϭ 46, JPax,Peq
40 Hz, 1 P, PCH3), 48 (dt, JPeq,Peq ϭ 102, JPeq,Pax ϭ 46 Hz, 1 P,
PPh2) ppm. C32H45CoP4 (612.5): calcd. C 62.75, H 7.40, P 20.23;
found C 62.72, H 7.38, P 20.39.
2
2
2
2
2
2
2
2
[{2-(Diphenylphosphanyl)styrene-(C,C-η2,P)}methylbis(trimethyl-
phosphane)cobalt(I)] (5): 2-(Diphenylphosphanyl)stryrene (571 mg,
[{2-(Diphenylphosphanyl)naphthyl-(C1,P)}(ethene)bis(trimethylphos-
1.98 mmol) in diethyl ether (40 mL) was mixed at Ϫ70 °C with
[CoCH3(PMe3)4] (750 mg, 1.98 mmol) in diethyl ether (40 mL).
phane)cobalt(
I)] (7): A sample of 2 (680 mg, 1.13 mmol) in diethyl
ether (50 mL) was stirred under 1 bar of ethene for 1 h to provide
After warming, the orange mixture was stirred at 20 °C for 3 h, a light red solution. The volatiles were removed in vacuo, and the
and the volume was then reduced to 40 mL. Pentane (50 mL) was
added with vigorous stirring to precipitate 5 as a light brown solid.
This was isolated by filtration and washing with pentane. Yield
solid residue was extracted with pentane (three 50-mL portions).
Crystallization at 4 °C afforded short orange rods of 7, suitable for
X-ray diffraction. Yield 506 mg (81%); m.p. 105Ϫ107 °C (dec.). 1H
2
652 mg (64%); m.p. 152Ϫ154 °C (dec.). 1H NMR (300 MHz, NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.90 (d, JP,H ϭ 6.5 Hz, 9
[D8]THF, 296 K): δ ϭ Ϫ0.85 (dt, 3JP,H ϭ 8.1, 1.8 Hz, CoCH3), 0.78
H, PCH3), 1.05 (d, JP,H ϭ 6.0 Hz, 9 H, PCH3), 1.49 (m, 2 H, ϭ
2
2
2
3
(d, JP,H ϭ 5.6 Hz, 9 H, PCH3), 1.30 (d, JP,H ϭ 5.5 Hz, 9 H, CH2), 2.47 (m, 2 H, ϭCH2), 6.95 (t, J ϭ 7.5 Hz, 2 H, CH), 7.15
3
PCH3), 1.80 (m, 2 H, ϭCH2), 2.64 (m, 1 H, ϭCH), 6.86 (t, J ϭ
(dd, 3J ϭ 6.8, 4J ϭ 1.6 Hz, 1 H, CH), 7.17 (dd, 3J ϭ 8.3, 4J ϭ
7.3 Hz, CH), 7.01 (dt, 3J ϭ 6.3, 4J ϭ 1.3 Hz, 1 H, CH), 7.18 (t, 1.3 Hz, 1 H, CH), 7.21 (dd, 3J ϭ 4.4, 4J ϭ 1.8 Hz, 1 H, CH),
3J ϭ 6.7 Hz, 1 H, CH), 7.26Ϫ7.31 (m, 6 H, CH), 7.31Ϫ7.33 (m, 1
7.26Ϫ7.33 (m, 7 H, CH), 7.46 (m, 2 H, CH), 7.54 (dd, J ϭ 7.6,
3
H, CH), 7.38Ϫ7.41 (m, 2 H, CH), 7.77Ϫ7.83 (m, 2 H, CH) ppm. 4J ϭ 1.8 Hz, 1 H, CH), 7.67Ϫ7.71 (m, 2 H, CH) ppm. 13C NMR
13C NMR (75.4 MHz, [D8]THF, 296 K): δ ϭ 17.6 (d, JP,C
ϭ
(75.4 MHz, [D8]THF, 296 K): δ ϭ 17.6 (d, 1JP,C ϭ 11.3 Hz, PCH3),
1
1
1
2
14.7 Hz, PCH3), 18.9 (d, JP,C ϭ 16.7 Hz, PCH3), 50.8 (s, ϭCH2), 20.3 (d, JP,C ϭ 18.8 Hz, PCH3), 25.4 (m, CH2), 40.1 (d, JP,C
62.1 (d, JP,C ϭ 18.2 Hz, ϭCH), 121.7 (d, JP,C ϭ 4.1 Hz, CH), 16.9 Hz, ϭCH2), 42.1 (d, JP,C ϭ 15.9 Hz, ϭCH2), 119.8 (s, CH),
123.4 (d, JP,C ϭ 112.6 Hz, CH), 126.4 (d, JP,C ϭ 7.9 Hz, CH),
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387
ϭ
2
4
2
2
3
3
124.4 (d, JP,C ϭ 5.4 Hz, CH), 125.9 (s, CH), 127.4 (s, CH), 127.6
1385

H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt
FULL PAPER
(d, JP,C ϭ 14.0 Hz, C), 127.9 (s, CH), 128.9 (d, JP,C ϭ 23.9 Hz,
1
1
2
2
2JPeq,Pax ϭ 48 Hz, 1 P, PCH3), 23 (dd, JPax,Peq ϭ 48, JPax,Peq
ϭ
CH), 132.6 (d, 2JP,C ϭ 10.7 Hz, CH), 133.1 (d, 3JP,C ϭ 7.3 Hz, CH), 48 Hz, 1 P, PCH3), 70 (dd, JPeq,Peq ϭ 81, JPeq,Pax ϭ 48 Hz, PPh2)
2
2
3
3
133.7 (d, JP,C ϭ 12.3 Hz, C), 141.2 (d, JP,C ϭ 6.4 Hz, CH), 145.8 ppm. C29H34CoOP3 (550.4): calcd. C 63.28, H 6.23, P 16.88; found
(m, C), 149.4 (s, C), 150.1 (s, C) ppm. 31P NMR (81 MHz,
C 62.67, H 5.78, P 17.30.
[D8]THF, 213 K): δ ϭ 4 (dd, JPeq,Pax ϭ 45, 2JPeq,Peq ϭ 36 Hz, 1 P,
2
[{2-(Diphenylphosphanyl)naphthyl-(C1,P)}iodobis(trimethyl-
phosphane)cobalt(II)] (10): A sample of 2 (670 mg, 1.12 mmol) in
diethyl ether (50 mL) was mixed at Ϫ70 °C with iodomethane
(365 mg, 2.57 mmol, slight excess). After 1 h at 20 °C, the mixture
was filtered and the solution was kept at 4 °C to afford dark-brown
crystals of 10. The solid was extracted with diethyl ether (two 80-
mL portions) to give a second fraction of 10, which was combined
with the first. Yield 421 mg (58%); m.p. 158Ϫ160 °C (dec.). Mag-
netic moment: µeff ϭ 1.91 µB. C28H34CoIP3 (649.3): calcd. C 51.79,
H 5.28, P 14.31; found C 51.78, H 5.41, P 14.26.
2
2
PCH3), 17 (dd, JPax,Peq ϭ 33, JPax,Peq ϭ 45 Hz, 1 P, PCH3), 75
(dd, 2JPeq,Pax ϭ 33, 2JPeq,Peq ϭ 36 Hz, 1 P, PPh2) ppm. C30H38CoP3
(550.4): calcd. C 65.46, H 6.96, P 16.88; found C 64.81, H 6.71,
P 17.27.
[{2-(Diphenylphosphanyl)-3-phenylphenyl-(C1,P)}(ethene)-
bis(trimethylphosphane)cobalt(I)] (8): A sample of 3 (940 mg, ca.
1.5 mmol) in THF (40 mL) was stirred under 1 bar of ethene for
3 h. The volatiles were removed in vacuo, and the oily residue was
extracted with pentane (50 mL). Crystallization at 4 °C afforded
short, orange rods of 8. Yield 503 mg (58%); m.p. 95Ϫ97 °C (dec.).
1H NMR (300 MHz, [D8]THF, 296 K): δ ϭ 0.82 (d, 2JP,H ϭ 6.3 Hz,
Crystal Structure Analyses: Crystal data are presented in Tables 1
and 2. Complex 1: A crystal was sealed under argon in a glass
capillary and mounted on a Bruker AXS P4 diffractometer. Reflec-
tions were collected (ω-scans) by use of graphite-monochromated
Mo-Kα radiation; a Lorentz polarization correction and an absorp-
tion correction based on ψ-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 idealized positions. Complex 4: Crys-
tal mounting, data collection, structure solution, and refinement
as for 1. Complex 7: Crystal mounting, data collection, structure
solution, and refinement as for 1. Two independent molecules per
asymmetric unit. Complex 9: Crystal mounting, data collection,
structure solution, and refinement as for 1. CCDC-184425 (1),
-184426 (4), -184427 (7), and -184428 (9) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
[or from the Cambridge Crystallographic Data Center, 12 Union
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223/336-
033; E-mail: deposit@ccdc.cam.ac.uk].
2
9 H, PCH3), 1.10 (d, JP,H ϭ 5.9 Hz, 9 H, PCH3), 1.66 (m, 1 H, ϭ
CH), 1.91 (m, 2 H, ϭCH2), 2.31 (m, 1 H, ϭCH), 6.51 (m, 1 H,
CH), 6.72 (dd, 3J ϭ 5.0, 4J ϭ 1.5 Hz, 2 H, CH), 7.15 (dd, 3J ϭ
4
3
4
6.8, J ϭ 1.6 Hz, 1 H, CH), 7.17 (dd, J ϭ 8.3, J ϭ 1.3 Hz, 1 H,
CH), 6.85 (m, 3 H, CH), 6.95 (dd, 3J ϭ 7.3, 4J ϭ 1.4 Hz, 1 H,
CH), 7.16 (dd, 3J ϭ 7.2, 4J ϭ 1.5 Hz, 1 H, CH), 7.21 (m, 6 H,
CH), 7.41(dd, 3J ϭ 9.4, 4J ϭ 1.5 Hz, 1 H, CH), 7.42 (m, 2 H, CH),
7.68 (dd, 3J ϭ 9.4, 4J ϭ 1.9 Hz, 1 H, CH), 7.70 (dd, 3J ϭ 5.8, 4J ϭ
2.6 Hz, 1 H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K):
1
1
δ ϭ 16.5 (d, JP,C ϭ 18.1 Hz, PCH3), 20.3 (d, JP,C ϭ 18.4 Hz,
2
2
PCH3), 32.5 (d, JP,C ϭ 10.4 Hz, ϭCH2), 38.8 (d, JP,C
ϭ
18.1 Hz, ϭCH2), 121.5 (s, CH), 124.7 (s, CH), 125.9 (s, CH), 126.6
(d, 2JP,C ϭ 8.8 Hz, CH), 127.1 (s, CH), 127.8 (s, CH), 128.2 (s, CH),
128.6 (d, 1JP,C ϭ 15.2 Hz, C), 131.9 (d, 2JP,C ϭ 12.1 Hz, CH), 132.2
2
1
(d, JP,C ϭ 12.2 Hz, CH), 135.6 (d, JP,C ϭ 16.4 Hz, CH), 136.9 (s,
C), 139.1 (d, 1JP,C ϭ 17.5 Hz, C), 140.7 (d, 3JP,C ϭ 4.3 Hz, C), 146.4
(s, C), 153.0 (m, CoC) ppm. 31P NMR (81 MHz, [D8]THF, 233 K):
2
2
δ ϭ Ϫ11 (dd, JPeq,Pax ϭ 47, JPeq,Peq ϭ 51 Hz, 1 P, PPh2), 9 (dd,
2
2
2JPax,Peq ϭ 31, JPax,Peq ϭ 47 Hz, 1 P, PCH3), 21 (dd, JPeq,Pax
ϭ
31, 2JPeq,Peq ϭ 51 Hz, 1 P, PCH3) ppm. C32H40CoP3 (576.2): calcd.
C 66.67, H 6.99, P 16.22; found C 66.45, H 7.41, P 16.14.
Table 1. Crystal data for compounds 1 and 4
[(Carbonyl){2-(diphenylphosphanyl)naphthyl-(C1,P)}bis(trimethyl-
phosphane)cobalt(I)] (9): A sample of 2 (770 mg, 1.28 mmol) in
1
4
THF (40 mL) was stirred under 1 bar of CO for 1 h to provide a
light red solution. The volatiles were removed in vacuo, and the
solid residue was extracted with pentane (three 70-mL portions).
Crystallization at Ϫ27 °C afforded short, orange rods of 9 suitable
Empirical formula
Molecular mass
Crystal size [mm]
Crystal system
C31H47CoP4
602.5
0.50 ϫ 0.45 ϫ 0.45 0.44 ϫ 0.40 ϫ 0.40
orthorhombic
P212121
10.929(3)
16.544(3)
17.501(9)
90
3164.3(19)
4
1.265
0.763
203(2)
C32H45CoP4
612.5
monoclinic
P21/c
for X-ray diffraction. Yield 616 mg (87%); m.p. 112Ϫ114 °C (dec.). Space group
˚
IR (Nujol): ν˜ ϭ 1905 cmϪ1 (CϵO). 1H NMR (300 MHz, [D8]THF,
a [A]
9.096(3)
35.594(3)
9.913(2)
98.79(2)
3171.8(13)
4
1.283
0.762
293(2)
4.6 Յ 2θ Յ 55
Ϫ1 Յ h Յ 11
Ϫ1 Յ k Յ 46
Ϫ12 Յ l Յ 12
8877
˚
2
b[A]
296 K): CO-eq isomer (12%): δ ϭ 0.68 (d, JP,H ϭ 6.3 Hz, 18 H,
PCH3), 1.12 (d, 2JP,H ϭ 7.9 Hz, 18 H, PCH3), 7.01Ϫ8.02 (m, 16 H,
˚
c [A]
β [°]
2
CH) ppm; CO-ax isomer (88%): δ ϭ 0.69 (d, JP,H ϭ 6.3 Hz, 9 H,
3
˚
V [A ]
PCH3), 1.00 (tЈ, |2JP,H
ϩ
4JP,H| ϭ 6.8 Hz, 18 H, PCH3), 1.19 (d,
Z
3
2JP,H ϭ 7.9 Hz, 9 H, PCH3), 7.08 (d, J ϭ 6.6 Hz, 1 H, CH), 7.10
Dcalcd. [g/cm3]
µ (Mo-Kα) [mmϪ1
Temperature [K]
(t, 3J ϭ 7.4 Hz, 1 H, CH), 7.26Ϫ7.29 (m, 8 H, CH), 7.43Ϫ7.49 (m,
]
3
3
4 H, CH), 7.61 (d, J ϭ 6.9 Hz, 1 H, CH), 7.70 (d, J ϭ 6.9 Hz, 1
3
3
H, CH), 7.84 (d, J ϭ 7.0 Hz, 1 H, CH), 7.97 (d, J ϭ 8.2 Hz, 1 Data coll. range [°]
4.7 Յ 2θ Յ 55
Ϫ1 Յ h Յ 14
Ϫ1 Յ k Յ 21
Ϫ1 Յ l Յ 22
H, CH) ppm. 13C NMR (75.4 MHz, [D8]THF, 296 K) CO-ax iso-
h
k
l
3
mer (88%): δ ϭ 19.8 (m, PCH3), 120.5 (s, C), 125.5 (d, JP,C
ϭ
5.4 Hz, CH), 125.8 (s, CH), 126.5 (s, C), 128.6 (d, 1JP,C ϭ 15.5 Hz,
No. reflect. measured 4975
2
C), 128.8 (d, JP,C ϭ 8.4 Hz, CH), 129.4 (s, CH), 130.4 (s, CH),
No. unique data
Parameters
4759 (Rint ϭ 0.0323) 7266 (Rint ϭ 0.0310)
335
1.010
0.0578
0.1243
2
1
132.6 (d, JP,C ϭ 12.7 Hz, CH), 133.3 (s, C), 134.7 (d, JP,C
ϭ
334
14.3 Hz, C), 138.9 (m, CH), 141.6 (s, C), 142.0 (s, C), 203.2 (s, CO)
GoF on F2
0.968
0.0484
0.1051
ppm. 31P NMR (81 MHz, [D8]THF, 233 K) COax isomer (12%):
R1 [I Ն 2σ(I)]
wR2 (all data)
2
2
δ ϭ 5 (d, JPeq,Peq ϭ 96 Hz, 2 P, PCH3), 63 (t, JPeq,Peq ϭ 96 Hz, 1
2
P, PPh2) ppm; COeq isomer (88%): δ ϭ Ϫ1 (dd, JPeq,Peq ϭ 81,
1386
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387

Five and Six-Membered Cobaltocycles with C,P-Chelating Ligands
FULL PAPER
Table 2. Crystal data for compounds 7 and 9
[1] [1a]
H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt, Eur. J. Inorg.
[1b]
Chem., 2003, 853Ϫ862.
H.-F. Klein, S. Schneider, M. He,
7
9
U. Flörke, H.-J. Haupt, Eur. J. Inorg. Chem. 2000, 2295Ϫ2301.
[2]
[3]
[2a] W. D. Jones, F. J. Feher, Acc. Chem. Res. 1989, 22, 91Ϫ100.
Empirical formula
Molecular mass
Crystal size [mm]
Crystal system
Space group
C30H38CoP3
550.4
0.40 ϫ 0.35 ϫ 0.30
monoclinic
P21/c
C29H34CoOP3
550.4
0.38 ϫ 0.15 ϫ 0.06
monoclinic
P21/c
18.242(2)
9.016(1)
18.301(2)
111.94(1)
2792.0(5)
4
1.309
0.806
293(2)
4.5 Յ 2θ Յ 50
Ϫ1 Յ h Յ 21
Ϫ1 Յ k Յ 10
Ϫ21 Յ l Յ 20
6135
[2b]
A. E. Shilov, G. B. Shul’pin, Chem. Rev. 1997, 97,
2879Ϫ2932.
J. M. Duff, B. L. Shaw, J. Chem. Soc., Dalton Trans. 1972,
2219Ϫ2225.
[4] [4a]
˚
M. A. Bennett, J. Chatt, E. Erskine, J. Lewis, R. F. Long,
a [A]
9.697(2)
[4b]
˚
R. S. Nyholm, J. Chem. Soc. A 1967, 501Ϫ509.
M. A.
b [A]
16.411(2)
35.970(6)
97.36(2)
5677.0(17)
8
1.288
0.790
˚
Bennett, E. J. Hann, R. N. Johnson, J. Organomet. Chem. 1977,
c [A]
[4c]
124, 189Ϫ211.
M. A. Bennett, R. N. Johnson, I. B.
β [°]
3
˚
Tomkins, J. Am. Chem. Soc. 1974, 96, 61Ϫ69.
H.-F. Klein, R. Beck, U. Flörke, H.-J. Haupt, Eur. J. Inorg.
Chem. 2002, 3305Ϫ3312.
V [ A ]
[5]
[6]
Z
Dcalcd. [g/cm3]
µ (Mo-Kα) [mmϪ1
]
T. A. Albright, J. K. Burdett, M. H. Whangbo, Orbital Interac-
tions in Chemistry, John Wiley & Sons, New York, 1985, p. 361.
Temperature [K]
293(2)
[7] [7a]
A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G.
Data coll. range [°]
4.2 Յ 2θ Յ 54
Ϫ12 Յ h Յ 1
Ϫ1 Յ k Յ 20
Ϫ45 Յ l Յ 45
Watson, R. Taylor, J. Chem. Soc., Dalton Trans. 1989, S1ϪS83.
[7b] H.-F. Klein, X. Li, U. Flörke, H.-J. Haupt, Z. Naturforsch.,
Teil B 2000, 55, 707Ϫ717.
h
k
l
[8] [8a]
H.-F. Klein, H. H. Karsch, Chem. Ber. 1976, 109,
No. reflect. measured 15436
[8b]
1453Ϫ1464.
38Ϫ42.
M. Bressan, P. Rigo, Inorg. Chem. 1975, 14,
No. unique data
Parameters
12400 (Rint ϭ 0.0584) 4910 (Rint ϭ 0.0378)
638
0.977
0.0665
0.1677
[8c]
W. P. Leung, H. K. Lee, L. H. Weng, Z. Y. Zhou,
313
GoF on F2
0.984
0.0469
0.1304
T. C. W. Mak, J. Chem. Soc., Dalton Trans. 1997, 779Ϫ783.
J. Blum, D. Gelinan, W. Baldossi, E. Shakh, A. Rosenfeld, Z.
Aizenshtat, J. Org. Chem. 1997, 62, 8681Ϫ8686.
[9]
R1 [I Ն 2σ(I)]
wR2 (all data)
[10]
[11]
´
F. H. Carre, C. Chuit, R. J. P. Corriu, W. E. Douglas, D. M.
H. Guy, C. Reye, Eur. J. Inorg. Chem. 2000, 647Ϫ653.
T. Bartik, T. Himmler, H.-G. Schulte, K. Seevogel, J. Or-
ganomet. Chem. 1984, 272, 29Ϫ41.
[12] [12a]
M. A. Bennett, R. S. Nyholm, J. D. Saxby, J. Organomet.
[12b]
Chem. 1967, 10, 301Ϫ306.
M. A. Bennett, W. R. Kneen,
R. S. Nyholm, J. Organomet. Chem. 1971, 26, 293Ϫ303.
H.-F. Klein, H. H. Karsch, Chem. Ber. 1975, 108, 944Ϫ954.
Received September 20, 2002
Acknowledgments
Financial support of this work by Fonds der Chemischen Industrie
is gratefully acknowledged.
[13]
[I02520]
Eur. J. Inorg. Chem. 2003, 1380Ϫ1387
1387