Oxidative addition of a diphosphine anhydride to iron(0) and nickel(0): A simple approach to installing four ligands

Article abstract of DOI:10.1021/om200073k

The diphosphine anhydride (PCO)₂O was prepared in high yield by DCC coupling of 2-diphenylphosphinobenzoic acid. The diphosphine oxidatively adds to Fe(0) carbonyls to give the acyl carboxylate Fe(PCO)(PCO ₂)(CO)₂ (1). The

Full text of DOI:10.1021/om200073k

NOTE
pubs.acs.org/Organometallics
Oxidative Addition of a Diphosphine Anhydride to Iron(0)
and Nickel(0): A Simple Approach to Installing
Four Ligands
Mark R. Ringenberg, Danielle L. Gray, and Thomas B. Rauchfuss*
Department of Chemistry, University of Illinois, 600 S. Mathews Avenue, Urbana, Illinois 61801, United States
S Supporting Information
b
ABSTRACT: The diphosphine anhydride (PCO)2O was prepared in high yield
by DCC coupling of 2-diphenylphosphinobenzoic acid. The diphosphine oxida-
tively adds to Fe(0) carbonyls to give the acyl carboxylate Fe(PCO)(PCO2)-
(CO)2 (1). The complex adopts a distorted octahedral geometry with trans
phosphines and cis carbonyl ligands. Treatment of Ni(COD)2 with (PCO)2O
afforded the square-planar acyl carboxylate Ni(PCO)(PCO2) (2) with trans
phosphine ligands. Upon treatment with PMe3, 1 gives the monocarbonyl Fe(PCO)(PCO2)(CO)(PMe3), whereas 2 and PMe3
react to give the pentacoordinate adduct 2PMe3. Both 1 and 2 give 1:1 adducts with B(C6F5)3 (BPhF ). Crystallographic analysis
3
revealed that the borane binds to the noncoordinated carboxylate oxygen in both cases. The value of νCO for the carboxylato ligand
decreased by 45 cmÀ1, and in the case of 1BPhF , νCO for the CO ligands increased by 15 cmÀ1. In solution, 1BPhF3 exists as an
3
equilibrium mixture of three isomers, including a kinetic isomer and another isomer that selectively crystallizes.
’ INTRODUCTION
oxidatively adds 2,3-dimethylsuccinic anhydride to give the acyl
carboxylato nickel(II) derivative (eq 1).8
Oxidative addition (OA) represents one of the most versatile
and predictable reactions in synthetic organometallic chemis-
try. Although myriad pathways exist for installing ligands, OA
provides a reliable method for installing two ligands in the
coordination sphere of a metal.1 First described in the 1970s,2
chelate-assisted oxidative addition typically installs three
ligands.2 Such reactions are of interest because the tritopic
attachment of the substrate drives OA reactions that are
unfavorable in the absence of chelation. Chelate-assisted
oxidative additions have received much attention in recent
years and have been applied to organic synthesis,3 including the
activation of CÀC bonds.4
’ RESULTS AND DISCUSSION
Phosphine Anhydride (PCO)2O. The (PCO)2O proligand
can be prepared in high yield by coupling of 2-diphenylpho-
sphinobenzoic acid using DCC (eq 2). It exists as a pale yellow,
air-stable solid that is sparingly soluble in most organic solvents.
The ligand is thermally stable in refluxing THF under an inert
atmosphere.
In this paper, we describe the OA of a diphosphine-function-
alized carboxylic acid anhydride to low-valent metals. This route
enables the installation of four ligands. Oxidative addition of the
diphosphine anhydride provides an easy way to generate highly
unsymmetrical coordination environments from simple reagents.
2-Diphenylphosphinobenzoic anhydride, abbreviated here as
(PCO)2O, had been previously generated in situ and used to
direct allylic substitution,5 but neither the ligand nor its com-
plexes have been previously characterized, despite the wide-
spread use of diphenylphosphinobenzoic acid.6 The oxidative
addition of carboxylic anhydrides is known in some cases to afford
metal acyl-carboxylates.7 For example, (TMEDA)Ni(COD)
Oxidative Addition of (PCO)2O to Fe(0) and Ni(0). Treat-
ment of (bda)Fe(CO)3 or Fe2(CO)9 with (PCO)2O afforded
the ferrous dicarbonyl 1 in good yield (bda = benzylidene
acetone). The 31P NMR and IR spectra of 1 indicate a single
unsymmetrical isomer (δ 45, 69, JPP = 125 Hz, eq 3). In the
related reaction involving (bda)Fe(CO)3, an intermediate was
detected with νCO = 1938 and 1893 cmÀ1 and possibly a higher
energy band obscured by the presence of 1 (νCO = 2024,
1966 cmÀ1). The 31P NMR spectrum of this intermediate
showed doublets at δ 49 and 64 (JPÀP = 125 Hz). Compounds
of the type Fe0(CO)3(PR3)2 exhibit comparable IR signatures,
e.g., Fe(CO)3(dppb): νCO =1981 (s), 1908 (m), 1879 (s).9
Received: January 28, 2011
Published: April 22, 2011
r
2011 American Chemical Society
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|

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NOTE
Figure 3. Structure of 2PMe3 with thermal ellipsoids shown at the 50%
probability level (hydrogen atoms omitted for clarity). Selected bond
lengths (Å): Ni11ÀC20: 1.871(11); Ni1ÀO1: 1.980(5); Ni1ÀP1:
2.217(2); Ni1ÀP2: 2.281(2); Ni1ÀP3: 2.259(8).
Figure 1. Structure of 1. Ellipsoids are shown at 50% probability
(hydrogen atoms are omitted for clarity). Selected bond lengths (Å):
Fe(1)ÀC(2): 1.741(4); Fe(1)ÀC(1): 1.805(4); Fe(1)ÀO(4): 2.004(2);
Fe(1)ÀC(3): 2.010(4); Fe(1)ÀP(2): 2.2565(10); Fe(1)ÀP(1):
2.2589(10).
Treatment of solutions of the cyclooctadiene complex Ni-
(COD)2 with 1 equiv of (PCO)2O afforded a single product,
Ni(PCO)(PCO2) (2, eq 4). According to the 31P NMR spectrum,
the phosphine ligands in this orange-colored product are
mutually trans. The value of JPP of 256 Hz indicates trans
phosphines,10 which was confirmed by crystallographic analysis.
The distorted square-planar geometry features P1ÀNiÀO1 and
P2ÀNiÀC20 angles of 89.95° and 86.84°, respectively 8° and 4°
wider than the corresponding bite angles in 1. The angles for
P1ÀNiÀP2 and C20ÀNiÀO1 are both 165°. The angle between
the two chelate rings (C20ÀNiÀP2 and O1ÀNiÀP1) is 20°.
PMe3 Derivatives. Both 1 and 2 react with PMe3. In the case
of 1, CO substitution was indicated, but in the case of 2 with
PMe3, we obtained the adduct, 2PMe3. Crystallographic
analysis of the 2PMe3 revealed a distorted trigonal-bipyrimidal
structure in which the three phosphine donors occupy the
equatorial positions. The sum of the angles of the three
PÀNiÀP angles is 359°, where P1ÀNi1ÀP2 is 121°, P2À
Ni1ÀP3 is 109°, and P3ÀNi1ÀP1 is 129°. The chelate angles
for P1ÀNi1ÀO1 are 86°, and P2ÀNi1ÀC20 is 87°; the axial
ligands are distorted by 6° from linearity. The complex
(PCO)Ni(PMe3)2I adopts a similarly distorted trigonal-bipyr-
imidal structure.11
Figure 2. Structure of 2 with thermal ellipsoids shown at the 50%
probability level (hydrogen atoms omitted for clarity). Selected
bond lengths (Å): Ni(1)ÀC(20):1.894(2); Ni(1)ÀO(1): 1.9151(16);
Ni(1)ÀP(2): 2.1786(6); Ni(1)ÀP(1): 2.1914(6).
Treatment of 1 with CO (1 atm) was found to induce partial
reductive elimination of (PCO)2O.
Adducts with Lewis Acids. Compound 1 rapidly formed a 1:1
adduct upon treatment with BPhF . That this adduct retains the
3
stereochemistry of the precursor is indicated by its 31P NMR
spectrum, which features doublets at δ 44 and 69 (JPÀP = 126
Hz). The IR spectrum showed Δ(νCO av
of 15 cmÀ1 upon
)
binding the borane. The value of νCdO for the carboxylato ligand
The molecular structure of 1 was determined crystallographi-
cally. The molecule can be described as the acyl-carboxylate
Fe(PCO)(PCO2)(CO)2. The complex adopts a distorted octa-
hedral geometry with a P1ÀFe1ÀP2 angle of 165.51(4)°. The
carboxylate and acyl groups are mutually cis, and the angle between
the two groups C(3)ÀFe(1)ÀO(4) is 89.40(12)°. The acylÀpho-
sphine P(1)ÀFe(1)ÀC(3) and carboxylateÀphosphine P(2)À
Fe(1)ÀO(4) chelate bite angles are respectively 80.97(10)°
and 80.20(7)°, with d(FeÀCacyl) = 2.011(4) and d(FeÀO) =
2.004(2) Å. The carboxylate and acyl groups are both trans to CO.
decreased by 45 cmÀ1, which can be compared to ΔνCdO of
49 cmÀ1 for the BPhF adduct of ethylbenzoate.12 Over the
3
course of several minutes in solution, 1BPhF converted to a
3
second isomer with cis phosphine ligands (JPÀP = 50 Hz).13 After
about 10 h, the 31P NMR spectrum featured yet another pair of
doublets at δ 46 and 57 (JPÀP = 69 Hz, Scheme 1). A second
equivalent of BPhF3 was found not to affect the rate of isomer-
ization. We also observed ready formation of the 1:1 adduct
2BPhF , which was spectroscopically characterized.
3
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NOTE
’ EXPERIMENTAL SECTION
General Considerations. Tris(pentafluorophenyl)borane was
purified by sublimation at 10 mTorr (90 °C).16 31P NMR shifts are
referenced to H3PO4 (δ 0).
2-Diphenylphosphinobenzoic Anhydride, (PCO)2O. A mix-
ture of 6.02 g (19.7 mmol) of 2-(diphenylphophino)benzoic acid17 and
2.23 g (10.8 mmol) of dicyclohexylcarbodiimide was treated with
100 mL of CH2Cl2. The solution immediately became yellow, con-
comitant with the precipitation of the dicyclohexylurea. After stirring for
3 h, the slurry was filtered through a plug of silica gel. The resulting
yellow solution was evaporated to yield a yellow powder, which was
washed with 20 mL of MeCN. Yield: 4.55 g (77%). 31P NMR (CH2Cl2):
δ À3.52. Anal. Calcd (found) for C36H30O3P2: C, 76.76 (76.17); H,
4.75 (4.82). IR (solid): νCO 1815 and 1757. Solutions of (PCO)2O in
THF oxidize upon exposure to air, as indicated by a 31P NMR signal at
δ 42; however, solid (PCO)2O appears to be indefinitely stable.
(2-Diphenylphosphinobenzoyl)(2-diphenylphosphino-
benzoato)iron(II)dicarbonyl, Fe(PCO)(PCO2)(CO)2 (1). A solu-
tion of 270 mg (0.947 mmol) of (bda)Fe(CO)3 (Fe2(CO)9 can be used
instead) in 20 mL of THF was added to a slurry of 324 mg (0.947 mmol) of
(PCO)2O in 10 mL of THF. The reaction solution was stirred under argon for
1 h at refluxing temperature. Solvent was removed at reduced pressure to yield
a yellow oil, which was triturated with 15 mL of pentane. The resulting yellow
powder was dissolved in 5 mL of CH2Cl2, and this solution was layered with
15 mL of pentane to yield crystals after being allowed to stand at À35 °C for
12 h. The yellow microcrystalline solid was collected by filtration and dried
under a stream of N2. Yield: 182 mg (30%). Anal. Calcd (found) for
C40H28FeO5P2(CH2Cl2): C, 59.78 (60.52); H, 3.68 (3.64). 31P NMR
(CH2Cl2): δ 45, 69 (d’s, JPÀP = 125 Hz). IR (CH2Cl2): νCO 2024,
1966 cmÀ1. X-ray crystals were obtained from vapor diffusion of pentane
into a solution of 1 in CH2Cl2. Treatment of 1 with PMe3 gave a new deri-
Figure 4. Structure of 1BPhF . Ellipsoids are shown at 50% probability.
3
For the sake of clarity, hydrogen atoms and the phenyl groups except the
ipso carbon centers are omitted. Selected bond lengths (Å): Fe(1)ÀC(2):
1.797(4); Fe(1)ÀC(1): 1.820(4); Fe(1)ÀC(20): 2.004(4); Fe(1)À
O(4): 2.023(3); Fe(1)ÀP(1): 2.2122(11); Fe(1)ÀP(2): 2.2964(11).
Scheme 1. Formation and Isomerization of 1BPhF
3
vative [31PNMR(CH2Cl2):δ64.4 (dd, JPÀP = 22, 129 Hz), 46.3 (dd, JPÀP
=
Crystals were obtained of the all-cis isomer of 1BPhF3 (Figure 4).
The crystallographic analysis showed that both carboxylate CÀO
bonds shorten by 0.05 Å compared with those in 1. Fe1ÀO1 bond
elongated by 0.019 Å. The d(B1ÀO5) of 1.531(5) Å indicates
22, 129 Hz), À1.81 (t, JPÀP = 22 Hz)], which was not characterized further.
(2-Diphenylphosphinobenzoyl)2-diphenylphosphino-
benzoatonickel, Ni(PCO2)(PCO) (2). A slurry of 1.32 g (2.218
mmol) of (PCO)2O in 20 mL of THF was added to a yellow solution of
610 mg (2.22 mmol) of Ni(COD)2 in 10 mL of THF. The reaction
solution was stirred for 2 h. During this time, the reaction solution
became orange and the (PCO)2O dissolved. The solution was concen-
trated to ∼10 mL and then diluted with 30 mL of pentane. The reaction
solution was cooled to À35 °C overnight, and the yellow-orange crystals
were collected by filtration. The product was washed with 2 Â ∼10 mL of
pentane and dried with a stream of N2. The product was recrystallized by
dissolution of the orange crystals in 5 mL of CH2Cl2; this solution was
layered with 30 mL of pentane and cooled to À35 °C. Yield: 1.36 g (94%).
Anal. Calcd (found) for C38H28NiO3P2: C, 69.12 (69.35); H, 4.27 (4.10).
31P NMR (CH2Cl2): δ14 (d, JPÀP = 256 Hz), 42 (d, JPÀP = 256 Hz).
(2-Diphenylphosphinobenzoyl)(2-diphenylphosphino-
benzoato)(trimethylphosphine)nickel(II), Ni(PCO)(PCO2)-
(PMe3), 2PMe3. A solution of 436 mg (0.668 mmol) of 2 in 30 mL of
THF was frozen in liquid nitrogen, and the head space was evacuated on
a high-vacuum manifold. Onto the frozen solution was condensed
∼0.1 mL of PMe3. The solution color changed from orange to red
almost immediately upon thawing. After stirring the reaction solution for
0.5 h, solvent and excess PMe3 were removed by distillation at reduced
pressure. The resulting red oil was trititurated with 20 mL of a 1:10
mixture of Et2OÀpentane to yield a red powder, which was collected by
filtration and washed with 10 mL of Et2O and 10 mL of pentane. The red
microcrystalline product was dried under a stream of N2 before being
extracted into 10 mL of CH2Cl2. Layering this extract with 20 mL of
pentane, followed by storing the flask at À35 °C, afforded red crystals,
which were washed with 10 mL of Et2O. Yield: 345 mg (71%). Anal.
Calcd (found) for C41H37NiO3P3: C, 67.19 (66.96); H, 5.10 (5.20).
a strong BÀO bond comparable to that in Ni(PCO2BPhF )-
3
(Me-allyl) (1.541(5) Å).14 BÀO bond distances in related borates
vary over a narrow range.12,15
Solutions freshly prepared from crystals of 1BPhF3 exhibited
signals for this cis isomer (δ 87, JPÀP = 50 Hz) and the starting
trans isomer; upon allowing the solution to stand, the third
isomer appeared.
’ CONCLUSIONS
The reaction of (PCO)2O with Fe(0) and Ni(0) reagents
installs two different bidentate ligands, κ2-(2-diphenylphos-
phinobenzoyl) (PCO) and κ2-(2-diphenylphosphinobenzoate)
(PCO2). In the case of the iron complex, the initial coordination
of the phosphine substituents can be detected prior to an
apparent intramolecular oxidative addition.
The coordination of Lewis acids to PCO2M centers has been
previously examined in the context of the SHOP catalysts.14 The
isomerization of the coordination sphere around Fe caused by
the attachment of a Lewis to a carboxylate is an unusual reaction.
This rearrangement reflects the dramatic influence of the borane
on the donor properties of the carboxylate ligand, consistent with
the resonance structures shown in eq 5.
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NOTE
31P NMR (CH2Cl2): δ À19 (dd, JPÀP = 152 Hz), 9.5 (dd, JPÀP = 152 Hz),
27 (t, JPÀP = 85 Hz). Upon standing at room temperature, samples decom-
posed to a new species, an apparent isomer: 31P NMR (CH2Cl2): δ 47.65
(JPÀP = 50 Hz), 41.43 (s), À14.65 (JPÀP = 50, 5 Hz). X-ray crystals were
obtained from vapor diffusion of pentane into a solution of 1 in CH2Cl2.
BPhF3 Adduct of 1. A solution of 70 mg (0.136 mmol) of BPhF3 in
5 mL of CH2Cl2 was added to a solution of 96 mg (0.134 mmol) of 1 in
10 mL of CH2Cl2. Upon addition of the borane, the color of the solution
turned from bright yellow to light orange. The reaction solution was
stirred for 0.5 h before concentrated to a volume of ∼5 mL. This
solution was layered carefully with pentane prior to cooling at À35 °C
for 12 h to yield X-ray quality crystals. Anal. Calcd (found) for C58H28-
BF15FeO5P2: C, 57.17 (56.05); H, 2.32 (2.35). 31P NMR (CH2Cl2): δ
39 (d, JPÀP= 50 Hz), 87 (d, JPÀP = 50 Hz). IR (CH2Cl2): νCO 2047,
K, R1(I > 2σ) = 0.0331, wR2(all data) = 0.0850 for 36 549 independent
reflections with a goodness-of-fit of 0.987.
Crystallography of 2PMe3. The highest peaks in the final
difference Fourier map were in the vicinity of the nickel atoms; the
final map had no other significant features. A final analysis of variance
between observed and calculated structure factors showed no depen-
dence on amplitude and little on resolution. For the data crystal, mean
I/σ(I) was less than 8 for reflections beyond 1 Å resolution. Reflections
between 1 and 0.8 Å resolution were removed from least-squares
refinement to improve the internal consistency. A structural model
consisting of the host plus two dichloromethane solvate molecules was
developed. Data for 2PMe3: Formula C43H41Cl4NiO3P3, M = 899.18,
orthorhombic, space group Pca21, a = 18.842(6), b = 25.205(12), c =
17.491(9) Å, V = 8307(6) Å3, Z = 8, Dc = 1.438 g cmÀ3, μ(Mo K) = 0.879
mmÀ3, F(000) = 3712, T = 193(2) K, R1(I > 2σ) = 0.0502, wR2(all data) =
0.1114 for 8646 independent reflections with a goodness-of-fit of 1.040.
1998, and 1988 cmÀ1. The isomerization of 1BPhF in CH2Cl2 was
3
monitored by IR spectroscopy over the course of 10 h. An adduct also
formed upon treatment of a CH2Cl2 solution of 2 with 1 equiv of
BPhF : 31P NMR (CH2Cl2, À44 °C): δ 44.00 and 8.9 (dd, 225 Hz).
’ ASSOCIATED CONTENT
3
Crystallography: General Comments. All structures were de-
termined by direct methods. The space group choice was confirmed by
successful convergence of the full-matrix least-squares refinement on F2.
Rigid-bond restraints (esd 0.01) were imposed on displacement param-
eters for disordered sites, and similar displacement amplitudes (esd 0.01)
were imposed on disordered sites overlapping by less than the sum of van
der Waals radii. Hydrogen atoms were included in the refinement as riding
idealized contributors, and their U’s were assigned as 1.2 times carrier Ueq.
Crystallography of 1. The highest peaks in the final difference Fourier
map were in the vicinity of atoms P1 and Fe1; the final map had no other
significant features. A final analysis of variance between observed and cal-
culated structure factors showed little dependence on amplitude and resolu-
tion. A structural model consisting of the host plus two disordered dichlor-
omethane solvate molecules was developed. All CÀCl distances were re-
strained as 1.76(1) Å (0.01 esd), and all Cl---Cl distances were restrained as
2.85(2) Å (esd 0.02). Data for 1: Formula C42H32Cl4FeO5P2, M = 876.27,
orthorhombic, space group Pbca, a = 17.3751(11), b = 19.2388(13), c =
23.6101(15) Å, V = 7892.3(9) Å3, Z = 8, Dc = 1.475 g cmÀ3, μ(Mo K) =
0.779 mmÀ3, F(000) = 3584, T = 193(2) K, R1(I > 2σ) = 0.0462, wR2(all
data) = 0.1068 for 7231 independent reflections with a goodness-of-fit
of 1.011.
S
Supporting Information. Spectroscopic and crystallo-
b
graphic information files (cif) are available free of charge via
the Internet at http://pubs.acs.org.
’ ACKNOWLEDGMENT
This research was supported by the Department of Energy.
We thank Dow Chemical for the gift of B(C6F5)3 and Dr. Aaron
Royer for advice.
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3
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3
space group P21/c, a= 15.6244(9), b= 17.9336(11), c= 22.4793(14) Å, β=
98.069(4)°, V = 6236.4(7) Å3, Z = 4, Dc = 1.569 g cmÀ3, μ(Mo K) = 0.644
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space group P1, a = 9.2924(7), b = 12.4785(10), c = 17.5116(14) Å, R =
88.217(5)°, β = 75.154(4)°, γ = 70.221(4)°, V = 1843.5(3) Å3, Z = 2,
qDc = 1.483 g cmÀ3, μ(Mo K) = 0.942 mmÀ3, F(000) = 844, T = 193(2)
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