Ni, Pd, Pt, and ru complexes of phosphine-borate ligands

Article abstract of DOI:10.1021/ic2026895

The species Cy₂PHC₆F₄BF(C ₆F₅)₂ reacts with Pt(PPh₃) ₄ to yield the new product cis-(PPh₃) ₂PtH(Cy₂PC₆F₄BF(C₆F ₅)₂) 1 via oxidative addition of the P-H bond of the phosphonium borate to Pt(0). The corresponding reaction with Pd(PPh ₃)₄ affords the Pd analogue of 1, namely, cis-(PPh ₃)₂PdH(Cy₂PC₆F₄BF(C ₆F₅)₂) 3; while modification of the phosphonium borate gave the salt [(PPh₃)₃PtH][(tBu₂PC ₆F₄BF(C₆F₅)₂)] 2. Alternatively initial deprotonation of the phosphonium borate gave [tBu ₃PH][Cy₂PC₆F₄BF(C₆F ₅)₂] 4, [SIMesH][Cy₂PC₆F ₄BF(C₆F₅)₂] 5 which reacted with NiCl₂(DME) yielding [BaseH]₂[trans-Cl ₂Ni(Cy₂PC₆F₄BF(C₆F ₅)₂)₂] (Base = tBu₃P 6, SIMes 7) or with PdCl₂(PhCN)₂ to give [BaseH]₂[trans- Cl₂Pd(Cy₂PC₆F₄BF(C₆F ₅)₂)₂] (Base = tBu₃P 8, SIMes 9). While [C₁₀H₆N₂(Me)₄H][tBu ₂PC₆F₄BF(C₆F₅) ₂] 10 was also prepared. A third strategy for formation of a metal complex of anionic phosphine-borate derivatives was demonstrated in the reaction of (COD)PtMe₂ with the neutral phosphine-borane Mes ₂PC₆F₄B(C₆F₅) ₂ affording (COD)PtMe(Mes₂PC₆F ₄BMe(C₆F₅)₂) 11. Extension of this reactivity to tBu₂PH(CH₂)₄OB(C ₆F₅)₃) was demonstrated in the reaction with Pt(PPh₃)₄ which yielded cis-(PPh₃) ₂PtH(tBu₂P(CH₂)₄OB(C ₆F₅)₃) 12, while the reaction of [SIMesH][tBu₂P(CH₂)₄OB(C₆F ₅)₃] 13 with NiCl₂(DME) and PdCl ₂(PhCN)₂ afforded the complexes [SIMesH] ₂[trans-Cl₂Ni(tBu₂PC₄H ₈OB(C₆F₅)₃)₂] 14 and [SIMesH]₂[trans-PdCl₂(tBu₂P(CH ₂)₄OB(C₆F₅)₃) ₂] 15, respectively, analogous to those prepared with 4 and 5. Finally, the reaction of 7 and 13with [(p-cymene)RuCl₂]₂ proceeds to give the new orange products [SIMesH][(p-cymene)RuCl ₂(Cy₂PC₆F₄BF(C₆F ₅)₂)] 16 and [SIMesH][(p-cymene)RuCl₂(tBu ₂P(CH₂)₄OB(C₆F₅) ₃)] 17, respectively. Crystal structures of 1, 6, 10, 11, 12, and 16 are reported.

Full text of DOI:10.1021/ic2026895

Article
pubs.acs.org/IC
Ni, Pd, Pt, and Ru Complexes of Phosphine-Borate Ligands
Stephanie L. Granville, Gregory C. Welch, and Douglas W. Stephan*
Department of Chemistry, University of Toronto, 80 St. George St. Toronto, Ontario, Canada M5S 3H6
S
* Supporting Information
ABSTRACT: The species Cy2PHC6F4BF(C6F5)2 reacts with Pt(PPh3)4 to yield
the new product cis-(PPh3)2PtH(Cy2PC6F4BF(C6F5)2) 1 via oxidative addition of
the P−H bond of the phosphonium borate to Pt(0). The corresponding reaction
with Pd(PPh3)4 affords the Pd analogue of 1, namely, cis-(PPh3)2PdH(Cy2PC6F4-
BF(C6F5)2) 3; while modification of the phosphonium borate gave the salt [(PPh3)3-
PtH][(tBu2PC6F4BF(C6F5)2)] 2. Alternatively initial deprotonation of the phosphonium
borate gave [tBu3PH][Cy2PC6F4BF(C6F5)2] 4, [SIMesH][Cy2PC6F4BF(C6F5)2]
5 which reacted with NiCl2(DME) yielding [BaseH]2[trans-Cl2Ni(Cy2PC6F4BF-
(C6F5)2)2] (Base = tBu3P 6, SIMes 7) or with PdCl2(PhCN)2 to give
[BaseH]2[trans-Cl2Pd(Cy2PC6F4BF(C6F5)2)2] (Base = tBu3P 8, SIMes 9). While [C10H6N2(Me)4H][tBu2PC6F4BF(C6F5)2]
10 was also prepared. A third strategy for formation of a metal complex of anionic phosphine-borate derivatives was
demonstrated in the reaction of (COD)PtMe2 with the neutral phosphine-borane Mes2PC6F4B(C6F5)2 affording
(COD)PtMe(Mes2PC6F4BMe(C6F5)2) 11. Extension of this reactivity to tBu2PH(CH2)4OB(C6F5)3) was demonstrated in the
reaction with Pt(PPh3)4 which yielded cis-(PPh3)2PtH(tBu2P(CH2)4OB(C6F5)3) 12, while the reaction of [SIMesH][tBu2P-
(CH2)4OB(C6F5)3] 13 with NiCl2(DME) and PdCl2(PhCN)2 afforded the complexes [SIMesH]2[trans-Cl2Ni(tBu2PC4H8OB-
(C6F5)3)2] 14 and [SIMesH]2[trans-PdCl2(tBu2P(CH2)4OB(C6F5)3)2] 15, respectively, analogous to those prepared with 4 and 5.
Finally, the reaction of 7 and 13 with [(p-cymene)RuCl2]2 proceeds to give the new orange products [SIMesH][(p-cymene)RuCl2-
(Cy2PC6F4BF(C6F5)2)] 16 and [SIMesH][(p-cymene)RuCl2(tBu2P(CH2)4OB(C6F5)3)] 17, respectively. Crystal structures of 1, 6,
10, 11, 12, and 16 are reported.
Scheme 1. Examples of Complexes Containing Anionic
Phosphine Ligands
INTRODUCTION
■
Neutral phosphine ligands are ubiquitous in transition metal
chemistry. On the other hand, anionic phosphine donors have
also garnered some attention. For example, a variety of hybrid
donor ligands including those incorporating phosphine-
carbon,1 phosphine-alkoxide,1e,2 phosphine-amide,3 phos-
phine-sulfonate4 or phosphine-thiolate5 donors have been
exploited in a range of coordination chemistry and in some
cases, catalysis. Anionic phosphines which provide a pendant
noncoordinating anion have also been explored as the proxi-
mity of the anion to a metal center impacts not only on sol-
ubility but also on the subsequent reactivity. Several strategies
to such ligands have been reported, and the subsequent chemi-
stry of such complexes has been explored. For example, sulfo-
nated triphenylphosphine has been employed to exploit the
chemistry of metal complexes in catalysis in water.6 In other
efforts to phosphines with pendant anions, Fu and co-workers7
have developed the chemistry of diphenylphosphidoborata-
benzene, [Ph2PBC5H5]− to prepare zwitterionic Zr, Fe, and
Rh complexes (Scheme 1). In related work, Manners and
co-workers have described Pt complexes of phosphine-borane
anions of the form [R2PBH3]− and [RHPBH3]− (Scheme 1).8
In a different approach, Peters and co-workers have developed a
family of complexes derived from the use of bis- and tris-
(phosphino)borates9 where these ligands provide a remote
borate anion (Scheme 1). Alternatively another strategy is based on
the use of neutral ambiphilic phosphine-borane species10 to ab-
stract a halide or an alkyl group from a metal thus generating the
pendant anion. For example, Bourissou et al. have exploited this
approach in the reaction of iPr2PC6H4BCy2 with [(Allyl)PdCl]2 to
give Pd−P and B−Cl bonds (Scheme 1),10h while Tilley and
co-workers have described the reactions of phosphinoethylbor-
anes with Ni-methyl species to give zwitterionic phosphine-
methylborate complexes (Scheme 1).11 Very recently Piers and
Jordan have described similar species derived from the coordination
of the anionic BF3 moiety adjacent the phosphine donors in the
anionic phosphine of the form F3BC6H4PR2(Scheme 1).12
Received: December 16, 2011
Published: March 29, 2012
© 2012 American Chemical Society
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Inorganic Chemistry
Article
were prepared by literature methods. (COD)PtMe2 were purchased
from the Aldrich Chemical Co.
Recently we have developed the chemistry of frustrated
Lewis pairs (FLPs); while most notably, these systems activate
H2, they have also been shown to activate a variety of mole-
cules, including: B−H bonds,13 disulfides,14 CO2,15 alkenes,16
dienes,17 alkynes,18 CO, azides,19 N2O,20 and most recently
NO.21 This work was initiated based on the synthesis of
zwitterions of the form R2PH(C6F4)BF(C6F5)2 which are
readily prepared from the combination of sterically bulky
secondary phosphines and B(C6F5)3 (Scheme 2). Analogous
Synthesis of cis-(PPh3)2PtH(Cy2PC6F4BF(C6F5)2) 1, [(PPh3)3PtH]-
[(tBu2PC6F4BF(C6F5)2)] 2, cis-(PPh3)2PdH(Cy2PC6F4BF(C6F5)2) 3, and
cis-(PPh3)2PtH(tBu2P(CH2)4OB(C6F5)3) 12. These compounds were
prepared in a similar fashion using analogous precursors and thus only
one preparation is detailed. A cloudy white solution of Cy2PHC6F4BF-
(C6F5)2 (0.114 g, 0.161 mmol) in toluene (5 mL) was added to an
orange solution of Pt(PPh3)4 (0.200 g, 0.161 mmol) in toluene
(5 mL). The reaction mixture was stirred at room temperature
overnight. The resulting cloudy orange solution was concentrated via
vacuum to 2 mL. Ten milliliters of pentane were added to precipitate a
pale peach solid. The solvent was decanted, and the solid washed with
3 × 5 mL of pentane and dried under vacuum.
Scheme 2. FLP Routes to Zwitterionic Phosphonium
Borates
1. Pale peach powder. Yield 198 mg (86%). Crystals suitable for
X-ray diffraction were grown from a layered C6D6 /cyclohexane
solution. 1H NMR (CD2Cl2): 7.34−7.11 (br m, 30H, P{C6H5}3),
1
2.33−1.16 (br m, 22H, P{C6H11}2), −6.73 (ddd, JH−Pt = 778 Hz,
2JH−P = 160, 17, 13 Hz, 1H, Pt-H). 11B NMR (CD2Cl2): −0.78 (br).
13C{1H} NMR (CD2Cl2) partial: 134.53 (d, JC−P = 12 Hz, Ar−C,
P{C6H5}3), 131.55 (d, JC−P = 10 Hz, Ar−C, P{C6H5}3), 128.87 (d, J =
11 Hz, Ar−C, P{C6H5}3), 30.82 (m, P{C6H11}2), 27.16 (d, JC−P
=
7 Hz, P{C6H11}2), 27.03 (d, JC−P = 6 Hz, P{C6H11}2), 26.45
(s, P{C6H11}2). 19F NMR (CD2Cl2): −130.41 (br s, 2F, C6F4),
−132.83 (br m, 3JF−F = 12 Hz, 2F, C6F4), −135.38 (br m, 4F, o-C6F5),
zwitterionic species are derived from reactions of such P/B
FLPs with THF or lactones resulting in ring opened products
(Scheme 2).22 These zwitterions are readily accessible in high
yields from commercially available precursors and provide easy
access to anionic phosphine donors. In this paper, we demons-
trate that these materials can be used to prepare a series of
zwitterionic phosphine-borate complexes of Ni, Pd, Pt, and Ru.
This work demonstrates that exploiting this FLP chemistry
provides a convenient avenue to anionic phosphines with
pendent noncoordinating anions.
3
3
−162.35 (t, JF−F = 20 Hz, 2F, p-C6F5), −166.81 (tm, JF−F = 20 Hz,
4F, m-C6F5), −192.65 (br s, 1F, B-F). 31P{1H} NMR (CD2Cl2): 28.98
1
3
1
(dd, JP−Pt = 2805 Hz, JP−P = 341, 19 Hz, PCy2), 22.01 (dd, JP−Pt
=
2290 Hz, 3JP−P = 20, 19 Hz, trans HPtPPh3), 18.16 (dd, JP−Pt = 2779
Hz, 3JP−P = 341, 20 Hz, cis HPtPPh3). Anal. Calcd for C66H53BF15P3Pt:
C, 55.44; H, 3.74; Found: C, 55.17; H, 3.91.
1
1
2. Pale peach powder. Yield 173 mg (78%). H NMR (CD2Cl2):
7.41−7.05 (br m, 45H, P{C6H5}3), 1.22 (d, JH−P = 13 Hz, 18H,
3
1
2
P{C(CH3)3}2), −5.76 (ddd, JH−Pt = 773 Hz, JH−P = 164, 18, 13 Hz,
1H, Pt-H). 11B NMR (CD2Cl2): −0.54 (br d, 1JB−F = 69 Hz). 13C{1H}
NMR (CD2Cl2) partial: 134.27 (t, JC−P = 6 Hz, P{C6H5}3), 131.84
(br d, JC−P = 6 Hz, P{C6H5}3), 131.42 (d, JC−P = 2 Hz, P{C6H5}3),
129.40 (s, P{C6H5}3), 129.24 (t, JC−P = 5 Hz, P{C6H5}3), 128.95
(d, J = 10 Hz, P{C6H5}3), 128.58 (s, P{C6H5}3), 125.66 (s, P{C6H5}3),
EXPERIMENTAL SECTION
■
All preparations were performed under an atmosphere of dry, O2-free
N2 employing both Schlenk line and inert atmosphere glovebox
techniques. Solvents (CH2Cl2, toluene, hexane, and pentane) were
purified employing a Grubbs’ type column system manufactured by
Innovative Technology. 1H, 11B, 13C{1H}, 19F, and 31P{1H} NMR
spectra were acquired on a Bruker Avance 400 MHz spectrometer,
a Varian Mercury 300 MHz spectrometer, or a Varian Mercury
1
4
30.61 (dd, JC−P = 19 Hz, JC−F = 3 Hz, P{C(CH3)3}2), 21.56
(s, P{C(CH3)3}2). 19F NMR (CD2Cl2): −124.68 (br s, 1F, C6F4),
3
−132.34 (br dm, JF−P = 109 Hz, 1F, C6F4), −135.48 (br m, 6F, 2F
C6F4 and 4F o-C6F5), −163.04 (t, 3JF−F = 20 Hz, 2F, p-C6F5), −167.17
(t, 3JF−F = 20 Hz, 4F, m-C6F5), −191.84 (br s, 1F, B-F). 31P{1H} NMR
1
3
(CD2Cl2): 23.14 (t, JP−Pt = 2220 Hz, JP−3P = 19 Hz, trans
1
HPt(PPh3)3), 22.90 (d, JP−Pt = 2819 Hz, JP−P = 19 Hz, cis
1
400 MHz spectrometer. H NMR resonances were referenced inter-
3
HPt(PPh3)3), 20.28 (br d, JP−F = 110 Hz, PtBu2). Anal. Calcd for
nally to the residual protonated solvent resonances, 13C resonances
were referenced internally to the deuterated solvent resonances, 11B,
19F and 31P resonances were referenced externally to 85% H3PO4,
BF3(Et2O), and CFCl3, respectively. 1H-13C HSQC and HMBC
experiments were carried out using conventional pulse sequences to
aid in the assignment of peaks in the 13C{1H} NMR spectra. Coupling
constants (J) are reported as absolute values. Spectral simulations of
selected second order 31P spectra were performed using the software
package MestReNova. All glassware was dried overnight at 120 °C and
evacuated for 1 h prior to use. Combustion analyses were performed
in-house employing a Perkin-Elmer 2400 Series II CHNS Analyzer.
UV−visible spectra were collected as 10−6 M solutions on a Agilent
Technology UV−visible spectrometer. ε is quoted in mol−1 cm−1. All
chemicals were purchased from Aldrich Chemical Co. or Strem
Chemical Co. and used without further purification. C6D6 and
cyclohexane were vacuum transferred from Na/benzophenone, and
freeze−pump−thaw degassed (×3). CD2Cl2 and C6D5Br were vacuum
transferred from CaH2, and freeze−pump−thaw degassed (×3). Hyflo
Super Cel (Celite) was purchased from Aldrich and dried for at least
12 h in a vacuum oven or on a Schlenk line prior to use. Molecular
sieves (4 Å) were purchased from Aldrich and dried at 100 °C under
vacuum using a Schlenk line. R2PHC6F4BF(C6F5)2 (R = Cy, tBu),
tBu2PH(CH2)4OB(C6F5)3,23 Mes2PC6F4B(C6F5)2,24 and SIMes25
C80H64BF15P4Pt: C, 58.58; H, 3.93; Found: C, 58.19; H, 4.49.
1
3. white powder. Yield 57 mg (64%). H NMR (CD2Cl2): 7.36−
7.16 (br m, 30H, P{C6H5}3), 2.21−1.16 (br m, 22H, P{C6H11}2),
2
−8.05 (ddd, JH−P = 175, 13, 6 Hz, 1H, Pd-H). 11B NMR (CD2Cl2):
−0.55 (br). 13C{1H} NMR (CD2Cl2) partial: 133.77 (br t, Ar−C,
P{C6H5}3), 130.94 (br s, Ar−C, P{C6H5}3), 130.86 (br s, Ar−C,
P{C6H5}3), 128.47 (br d, Ar−C, P{C6H5}3), 30.32 (m, P{C6H11}2),
26.17 (br d, P{C6H11}2), 26.12 (s, P{C6H113}2). 19F NMR (CD2Cl2):
−131.85 (br s, 2F, C6F4), −133.71 (br m, JF−P = 12 Hz, 2F, C6F4),
−136.39 (br m, 4F, o-C6F5), −163.36 (t, 3JF−F = 20 Hz, 2F, p-C6F5),
3
−167.83 (tm, JF−F = 20 Hz, 4F, m-C6F5), −193.40 (br s, 1F, B-F).
3
3
31P{1H} NMR (CD2Cl2): 31.09 (ddt, JP−P = 343, 28 Hz, JF−P
=
3
12 Hz, PCy2), 24.02 (dd, JP−P = 343, 29 Hz, cis HPdPPh3) 20.45
3
(ddt, JP−P = 29, 28 Hz, trans HPdPPh3). Anal. Calcd for
C66H53BF15P3Pd: C, 59.10; H, 3.98; Found: C, 57.2726; H, 4.09.
12. pale peach powder. Yield 71 mg (84%). Crystals suitable for
X-ray diffraction were grown from a layered C6D6/pentane solution.
1H NMR (CD2Cl2): 7.40−7.05 (br m, 30H, P{C6H5}3), 2.88 (br s,
3
2H, CH2CH2O), 1.54 (br s, 4H, CH2CH2CH2O), 1.28 (d, JH−P
=
14 Hz, 18H, P{C(CH3)3}2), 0.87 (br s, 2H, PCH2CH2), −6.92
1
2
(ddd, JH−Pt = 786 Hz, JH−P = 162, 14, 14 Hz, 1H, Pt-H). 11B NMR
(CD2Cl2): −2.94 (s). 13C{1H} NMR (CD2Cl2) partial: 134.34
(br d, JC−P = 40 Hz, Ar−C, P{C6H5}3), 131.33 (br d, JC−P = 26 Hz,
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Ar−C, P{C6H5}3), 129.11 (d, JC−P = 10 Hz, Ar−C, P{C6H5}3), 128.83
(d, JC−P = 11 Hz, Ar−C, P{C6H5}3), 63.14 (s, CH2CH2O), 37.18
C84H100B2Cl2F30NiP4: C, 51.61; H, 5.16; Found: C, 50.76;18 H,
5.40. UV−vis: λmax (ε)/nm 382 (6096).
1
1
1
7. Pink powder. Yield 119 mg (75%). H NMR (CD2Cl2): 7.76
(d, JC−P = 27.5 Hz, P{C(CH3)3}2), 34.08 (d, JC−P = 16 Hz,
PCH2CH2), 30.01 (br d, P{C(CH3)3}2), 23.23 (s, CH2CH2O), 21.16
(s, 2H, NCHN), 6.98 (s, 8H, m-MesAr-H), 4.25 (s, 8H, NCH2CH2N),
2.44−1.29 (br m, 4H, P{C6H11}2), 2.29 (s, 12H, Mes-p-CH3), 2.23
(s, 24H, Mes-o-CH3). 11B NMR (CD2Cl2): −0.76 (br). 13C{1H} NMR
(CD2Cl2) partial: 158.90 (s, NCHN), 141.65 (s, ipso-MesAr−C-N),
135.22 (s, o-MesAr−C), 130.42 (s, m-MesAr−C), 129.93 (s, p-
MesAr−C), 51.70 (s, NCH2CH2N), 32.33 (br s, P{C6H11}2), 29.75
(br s, P{C6H11}2), 28.94 (br s, P{C6H11}2), 27.51 (br s, P{C6H11}2),
21.09 (s, Mes-p-CH3), 17.59 (s, Mes-o-CH3). 19F NMR (CD2Cl2):
−134.75 (br m, 8F, C6F4), −135.52 (br m, 8F, o-C6F5), −162.35
3
(s, PCH2CH2). 19F NMR (CD2Cl2): −133.80 (d, JF−F = 25 Hz, 6F,
3
3
o-C6F5), −163.96 (t, JF−F = 20 Hz, 3F p-C6F5), −167.43 (t, JF−F
=
=
19 Hz, 6F, m-C6F5). 31P{1H} NMR (CD2Cl2): 56.52 (dd, JP−Pt
1
3
1
2729 Hz, JP−P = 314, 17 Hz, PtBu2), 21.58 (dd, JP−Pt = 2247 Hz,
3JP−P = 20, 17 Hz, trans HPtPPh3), 18.38 (dd, 1JP−Pt = 2569 Hz, 3JP−P
=
314, 20 Hz, cis HPtPPh3). Anal. Calcd for C66H57BF15OP3Pt: C, 55.13;
H, 4.02; Found: C, 55.19; H, 4.32.
Synthesis of [BaseH][Cy2PC6F4BF(C6F5)2] (Base = tBu3P 4,
SIMes 5). These compounds were prepared in a similar fashion and
thus only one preparation is detailed. A clear, colorless solution of
t-Bu3P (0.057 g, 0.282 mmol) in toluene (4 mL) was added to a white
slurry of Cy2PHC6F4BF(C6F5)2 (0.200 g, 0.282 mmol) in toluene
(4 mL). The resulting reaction mixture was stirred at room
temperature overnight. All volatiles were removed via vacuum from
the clear, colorless solution. The residue was washed with 4 × 5 mL of
pentane and dried via vacuum.
3
(t, JF−F = 20 Hz, 4F, p-C6F5), −166.82 (br m, 8F, m-C6F5), −191.01
(br s, 2F, B-F).31P{1H} NMR (CD2Cl2): 10.60 (br s, PCy2). Anal.
Calcd for C102H98B2Cl2F30N4NiP2: C, 56.64; H, 4.57; N, 2.59; Found:
C, 55.94;18 H, 4.78; N, 2.47. UV−vis: λmax (ε)/nm 382 (8525).
Synthesis of [tBu3PH]2[trans-Cl2Pd(Cy2PC6F4BF(C6F5)2)2] 8,
[SIMesH]2[trans-PdCl2(Cy2PC6F4BF(C6F5)2)2] 9, and [SIMesH]2-
[trans-PdCl2(tBu2P(CH2)4OB(C6F5)3)2] 15. These compounds were
prepared in a similar fashion and thus only one preparation is detailed.
A solution of PdCl2(PhCN)2 (0.014 g, 0.037 mmol) in dichloro-
methane (3 mL) was added to a solution of 5 (0.0668 g, 0.073 mmol)
in dichloromethane (3 mL). The reaction mixture was stirred at room
temperature overnight to give a clear, bright yellow solution. The
reaction mixture was concentrated to 1 mL under vacuum. Ten
milliliters of pentane were added to precipitate a yellow solid. The
solvent was decanted, and the solid washed with a further 5 mL of
pentane and dried under vacuum. The final product was a pale yellow
powder.
4. white powder. Yield 240 mg (93%). 1H NMR (C6D6): 6.09
1
(d, JH−P = 472 Hz, 1H, H-P{C(CH3)3}3), 2.39−1.08 (br m, 22 H,
3
P{C6H11}2), 0.79 (d, JH−P = 15 Hz, 18H, H−P{C(CH3)3}3). 11B
1
NMR (C6D6): 0.16 (br). 13C{1H} NMR (CD2Cl2): 37.86 (d, JC−P
=
28 Hz, P{C(CH3)3}3), 30.41 (s, P{C(CH3)3}3), 27.58 (s, P{C6H11}2),
27.53 (d, JC−P = 6 Hz, P{C6H11}2), 27.41 (d, P{C6H11}2), 26.87 (s,
P{C6H11}2). 19F NMR (C6D6): −132.42 (br m, 2F, C6F4), −134.21
3
(br m, 2F, C6F4), −134.54 (m, 4F, o-C6F5), −160.87 (t, 2F, JF−F
=
3
21 Hz, p-C6F5), −165.72 (td, 4F, JF−F = 21, 8 Hz, m-C6F5), −181.13
(br s, 1F, B-F). 31P{1H} NMR (C6D6): 48.99 (s, 1P, HPtBu3), −10.37
(t, 3JP−F = 38 Hz, 1P, PCy2). Anal. Calcd for C42H50BF15P2: C, 55.28;
H, 5.52; Found: C, 55.45; H, 5.63.
8. Yield 59 mg (81%). 1H NMR (CD2Cl2): 5.55 (d, 1JH−P = 446 Hz,
2H, H-P{C(CH3)3}3), 2.30−1.19 (br m, 44H, P{C6H11}2), 1.56
3
(d, JH−P = 16 Hz, 54H, H−P{C(CH3)3}3). 11B NMR (CD2Cl2):
−0.32 (br). 13C{1H} NMR (CD2Cl2) partial: 37.40 (d, 1JC−P = 27 Hz,
P{C(CH3)3}3), 29.96 (s, P{C(CH3)3}3), 32.75 (s, P{C6H11}2), 29.51
(s, P{C6H11}2), 28.83 (s, P{C6H11}2), 27.27 (d, JC−P = 7 Hz,
P{C6H11}2), 26.51 (s, P{C6H11}2). 19F NMR (CD2Cl2): −129.30 (br s,
4F, C6F4), −135.42 (br dm, 4F, C6F4), −136.19 (br m, 8F, o-C6F5),
1
5. white powder. Yield 660 mg (92%). H NMR (CD2Cl2): 8.19
(s, 1H, NCHN), 7.01 (s, 4H, m-MesAr-H), 4.42 (s, 4H, NCH2CH2N),
2.32 (s, 18H, Mes-CH3), 2.20−1.12 (br m, 22 H, P{C6H11}2). 11B
NMR (CD2Cl2): −0.49 (br). 13C{1H} NMR (CD2Cl2) partial: 160.36
(s, NCHN), 141.77 (s, ipso-MesAr-C-N), 135.40 (s, o-MesAr-C),
130.61 (s, m-MesAr-C), 130.30 (s, p-MesAr-C), 51.96 (s, NCH2-
CH2N), 32.44 (br m, P{C6H11}2), 29.81 (s, P{C6H11}2), 28.98
(s, P{C6H11}2), 27.75 (br m, P{C6H11}2), 27.56 (br m, P{C6H11}2),
3
3
−163.37 (t, 4F, JF−F = 20 Hz, p-C6F5), −167.76 (t, 8F, JF−F = 20,
7 Hz, meta-C6F5), −189.45 (br s, 2F, B-F). 31P{1H} NMR (CD2Cl2):
55.96 (s, 2P, PtBu3), 25.75 (s, 2P, PCy2). Anal. Calcd for
C84H100B2Cl2F30P4Pd: C, 50.38; H, 5.03; Found: C, 50.67; H, 5.37.
26.81 (s, P{C6H11}2), 21.29 (s, Mes-p-CH3), 17.91 (s, Mes-o-CH3). 19
F
1
9. Beige powder. Yield 77 mg (47%). H NMR (CD2Cl2): 7.85
NMR (CD2Cl2): −133.80 (m, 2F, C6F4), −135.81 (m, 2F, C6F4),
(s, 2H, NCHN), 6.98 (s, 8H, m-MesAr-H), 4.33 (s, 8H, NCH2CH2N),
2.77 (br m, 4H, P{C6H11}2), 2.30 (s, 12H, Mes-p-CH3), 2.26 (s, 24H,
Mes-o-CH3), 2.14−1.67 (br m, 40 H, P{C6H11}2). 11B NMR
(CD2Cl2): −0.82 (br). 13C{1H} NMR (CD2Cl2) partial: 158.91
(s, NCHN), 141.65 (s, ipso-MesAr−C-N), 135.37 (s, o-MesAr−C),
130.46 (s, m-MesAr−C), 130.07 (s, p-MesAr−C), 51.82 (s, NCH2-
CH2N), 32.96 (m, P{C6H11}2), 29.75 (d, JC−P = 3 Hz, P{C6H11}2),
28.99 (d, JC−P = 3 Hz, P{C6H11}2), 27.52 (s, P{C6H11}2), 21.14
3
−135.67 (m, 4F o-C6F5), −162.64 (t, 2F, JF−F = 21 Hz, p-C6F5),
3
−166.92 (td, 4F, JF−F = 21, 4.75 Hz, m-C6F5), −189.90 (br s, 1F,
B-F). 31P{1H} NMR (CD2Cl2): −10.69 (t, 3JP−F = 35 Hz, PCy2). Anal.
Calcd for C51H49BF15N2P: C, 60.25; H, 4.86; N, 2.76; Found: C,
60.51; H, 5.21; N, 3.18.
Synthesis of [BaseH]2[trans-Cl2Ni(Cy2PC6F4BF(C6F5)2)2] (Base =
tBu3P 6, SIMes 7). These compounds were prepared in a similar
fashion and thus only one preparation is detailed. A solution of 4
(0.075 g, 0.082 mmol) in CH2Cl2 (4 mL) was added to a solution of
NiCl2(DME) (0.0099 g, 0.045 mmol) in CH2Cl2 (4 mL). The reaction
mixture was stirred at room temperature overnight to give an opaque
pink/purple solution. The mixture was filtered through glass wool, and
the resulting clear pink/purple solution was concentrated to 1 mL via
vacuum. Twelve milliliters of pentane were added to precipitate a pink
solid, which was washed with 5 mL of pentane and dried via vacuum.
6. Pink powder. Yield 58 mg (73%). Crystals suitable for X-ray
diffraction were grown from a layered CH2Cl2/pentane solution.
(s, Mes-p-CH3), 17.66 (s, Mes-o-CH3). 19F NMR (CD2Cl2): −134.62
3
(br s, 8F, C6F4), −135.52 (br m, 8F o-C6F5), −162.35 (t, 4F, JF−F
=
3
20 Hz, p-C6F5), −167.17 (dt, 8F, JF−F = 20, 5 Hz, m-C6F5), −191.26
(br s, 2F, B-F). 31P{1H} NMR (CD2Cl2): 26.05 (s, PCy2). Anal. Calcd
for C102H98B2Cl2F30N4P2Pd: C, 55.42; H, 4.47; N, 2.53; Found: C,
55.86; H, 4.51; N, 2.63.
1
15. Pale yellow powder. Yield 77 mg (47%). H NMR (CD2Cl2):
8.00 (s, 2H, NCHN), 7.03 (s, 8H, m-MesAr-H), 4.44 (s, 8H,
NCH2CH2N), 3.01 (br s, 4H, CH2CH2O), 2.33 (s, 24H, Mes-o-CH3),
2.31 (s, 12H, Mes-p-CH3), 1.76 (br s, 8H, PCH2CH2CH2), (1.61 (br s,
4H, PCH2CH2), 1.37 (t, 36H, 3JH−P = 6 Hz, P{C(CH3)3}2). 11B NMR
(CD2Cl2): −3.02 (s). 13C{1H} NMR (CD2Cl2) partial: 160.76 (s,
1
1H NMR (CD2Cl2): 5.48 (d, JH−P = 445 Hz, 2H, H-P{C(CH3)3}3),
2.20−1.29 (br m, 44H, P{C6H11}2), 1.54 (d, 3JH−P = 16 Hz, 54H, H−
P{C(CH3)3}3). 11B NMR (CD2Cl2): δ −0.76 (br). 13C{1H} NMR
NCHN), 141.90 (s, ipso-MesAr−C-N), 135.13 (s, o-MesAr−C),
1
2
(CD2Cl2) partial: 37.55 (d, JC−P = 27 Hz, P{C(CH3)3}3), 30.34
130.60 (s, m-MesAr−C), 130.01 (s, p-MesAr−C), 63.93 (d, JC−B
=
1
(s, P{C(CH3)3}3), 29.96 (s, P{C6H11}2), 29.28 (s, P{C6H11}2), 27.88
7 Hz, CH2CH2O), 61.04 (d, JC−P = 10 Hz, PCH2CH2), 51.87
(s, NCH2CH2N), 30.85 (br m, P{C(CH3)3}2), 30.76 (br d,
P{C(CH3)3}2), 23.44 (s, CH2CH2O), 22.77 (s, PCH2CH2), 21.15
(s, Mes-p-CH3), 17.79 (s, Mes-o-CH3). 19F NMR (CD2Cl2): −133.80
3
(d, JC−P = 7 Hz, P{C6H11}2), 27.02 (s, P{C6H11}2). 19F NMR
(CD2Cl2): −128.05 (br m, 4F, C6F4), −134.65 (br s, 4F, C6F4),
−135.25 (br s, 8F o-C6F5), −162.44 (br m, 4F, p-C6F5), −166.81 (br s,
8F, m-C6F5), −188.99 (br s, 2F, B-F). 31P{1H} NMR (CD2Cl2): 56.33
(s, 2P, H-PtBu3), 10.17 (s, 2P, PCy2). Anal. Calcd for
3
3
(br d, JF−F = 22 Hz, 4F, o-C6F5), −163.90 (t, JF−F = 20 Hz, 2F,
p-C6F5), −167.29 (t, JF−F = 20 Hz, 4F, m-C6F5). 31P{1H} NMR
3
4713
dx.doi.org/10.1021/ic2026895 | Inorg. Chem. 2012, 51, 4711−4721

Inorganic Chemistry
Article
1
(CD2Cl2): 40.61 (br s, PtBu2). Anal. Calcd for C102H106B2Cl2F30-
N4O2P2Pd: C, 54.43; H, 4.75; N, 2.49; Found: C, 54.19; H, 4.95; N,
2.41.
18H, JH−P = 10.65 Hz, P{C(CH3)3}2). 11B NMR (CD2Cl2): −3.00
(s). 13C{1H} NMR (CD2Cl2) partial: 159.31 (s, NCHN), 142.07
(s, ipso-MesAr−C-N), 135.01 (s, o-MesAr−C), 130.68 (s, m-MesAr−C),
129.76 (s, p-MesAr−C), 51.86 (s, NCH2CH2N), 64.43 (s, CH2-
Synthesis of [C10H6N2(Me)4H][tBu2PC6F4BF(C6F5)2] 12. To a
slurry of tBu2PH(C6F4)BF(C6F5)2 (0.050 g, 0.076 mmol) in benzene
(2 mL) was added a solution of proton sponge (0.016 g, 0.075 mmol)
in benzene (1 mL). The reaction was allowed to stir for 30 min at
which time all volatiles were removed in vacuo to give a white solid.
Yield 60 mg (91%). Crystals suitable for X-ray diffraction were grown
via slow evaporation of a concentrated benzene solution at 25 °C.
1
CH2O), 34.91 (d, JC−P = 12 Hz, PCH2CH2), 21.64 (s, CH2CH2O),
2
1
21.46 (d, JC−P = 5 Hz, PCH2CH2), 31.21 (d, JC−P = 21 Hz,
P{C(CH3)3}2), 29.68 (d, 1JC−P = 14 Hz, P{C(CH3)3}2), 21.10 (s, Mes-
p-CH3), 17.76 (s, Mes-o-CH3). 19F NMR (CD2Cl2): −133.86 (br d,
3JF−F = 22 Hz, 6F, o-C6F5), −164.05 (t, JF−F = 20 Hz, 3F, p-C6F5),
3
−167.39 (br t, JF−F = 20 Hz, 6F, m-C6F5). 31P{1H} NMR (CD2Cl2):
3
3
1H NMR (C6D6): 18.16 (s, 1H, NH), 7.39 (d, JH−H = 8 Hz, 2H,
28.46 (s, 1P, PtBu2). Anal. Calcd for C51H53BF15N2OP + 0.6 equiv of
toluene: C, 60.71; H, 5.33; N, 2.56; Found: C, 60.63; H, 5.52; N, 2.69.
Synthesis of [SIMesH]2[trans-Cl2Ni(tBu2P(CH2)4OB(C6F5)3)2] 14.
A solution of NiCl2(DME) (0.011 g, 0.049 mmol) in CH2Cl2 (3 mL)
was added to a solution of 13 (0.100 g, 0.096 mmol) in CH2Cl2
(3 mL). After stirring at room temperature for 10 min, the reaction
mixture began to change color from yellow to green. Stirring was
continued overnight to give an opaque blue solution. The solution was
filtered through glass wool to remove any unreacted NiCl2(DME).
Volatiles were removed from the filtrate via vacuum. The blue oily
residue was washed with 2 × 5 mL of pentane, redissolved in 2 mL of
toluene and precipitated with 10 mL of pentane. The residue was again
dissolved in 5 mL of CH2Cl2, filtered through glass wool, and all
volatiles were removed via vacuum to give a blue oil. Five milliliters of
hexane were added, and the mixture stored in the freezer at −35 °C.
C10H6), 7.08 (t, 3JH−H = 8 Hz, 2H, C10H6), 6.84 (d, 3JH−H = 8 Hz, 2H,
1
C10H6), 2.31 (s, 12H, {N(CH3)2}2), 1.25 (d, JH−P = 14 Hz, 18H,
P{C(CH3)3}2). 11B{1H} NMR (C6D6): −0.78 (br). 13C{1H} NMR
(C6D6) partial: 149.20 (dm, 1JC−F = 230 Hz, CF), 148.76 (dm, 1JC−F
=
240 Hz, CF), 147.37 (dm, 1JC−F = 240 Hz, CF), 143.74 (s, quaternary,
1
C10H6N2(CH3)4H), 139.48 (dm, JC−F = 245 Hz, CF), 137.10 (dm,
1JC−F = 250 Hz, CF), 135.68 (s, quaternary, C10H6N2(CH3)4H),
129.43 (s, o-C10H6N2(CH3)4H), 126.97 (s, m-C10H6N2(CH3)4H),
120.81 (s, p-C10H6N2(CH3)4H), 118.68 (s, quaternary,
1
C10H6N2(CH3)4H), 45.29 (s, N(CH3)2), 32.71 (d, JC−P = 28 Hz,
2
P{C(CH3)3}2), 30.55 (d, JC−P = 20 Hz, P{C(CH3)3}2). 19F NMR
(C6D6): −123.92 (ddd, 1F, 3JF−F(D) = 38 Hz, 3JF−P = 21 Hz, 4JF−F(B)
=
3
3
14 Hz, C6F4 A), −130.99 (ddd, 1F, JF−P = 110 Hz, JF−F(C) = 24 Hz,
4JF−F(A) = 14 Hz C6F4 B), −134.56 (ddd, 1F, 3JF−F(B) = 24 Hz, 4JF−P
=
1
The final product was a blue powder. Yield 78 mg (72%). H NMR
4
14 Hz, JF−P = 7 Hz, C6F4 C), −134.91 (m, 1F, C6F4 D), −134.91
(CD2Cl2): δ 9.37 (s, 2H, NCHN), 7.20 (s, 8H, m-MesAr-H), 5.37
(s, 8H, NCH2CH2N), 3.34 (br s, 4H, CH2CH2O), 2.83 (br s, 4H,
CH2CH2O), 2.61 (s, 12H, Mes-p-CH3), 2.43 (s, 24H, Mes-o-CH3),
2.27 (br s, 4H, PCH2CH2), 1.81 (br s, 4H, PCH2CH2), 1.61 (d, 36H,
3JH−P = 16 Hz, P{C(CH3)3}2). 11B NMR (CD2Cl2): δ −2.41 (s),
−2.93 (s). 13C{1H} NMR (CD2Cl2) partial: δ 168.50 (s, 2C, NCHN),
142.06 (s, ipso-MesAr−C-N), 136.18 (s, p-MesAr−C), 131.53
(s, m-MesAr−C and o-MesAr−C), 64.34 (br d, PCH2CH2), 63.84
(br d, CH2CH2O), 33.63 (s, CH2CH2O), 33.28 (s, PCH2CH2), 28.49
3
3
(dm, 4F, JF−F = 15 Hz, o-C6F5), −161.51 (t, 2F, JF−F = 20 Hz ,
p-C6F5), - 166.17 (ddd, 4F, 3JF−F = 20 Hz, 3JF−F = 15 Hz, 6JF−F = 9 Hz
meta-C6F5), −190.63 (br s, 1F, ArF BF). 31P{1H} NMR (C6D6): δ
3
3
3
5
21.67 (dddd, JP−F(B) = 110 Hz, JP−F(A) = 21 Hz, JP−F(C) = 7 Hz,
5JP−F(D) = 5 Hz). Anal. Calcd. for C40H37BF15N2P: C, 55.06; H, 4.27;
N, 3.21. Found: C, 55.11; H, 4.37; N, 3.07%.
Synthesis of (COD)PtMe(Mes2PC6F4BMe(C6F5)2) 11. To a vial
charged with (COD)PtMe2 (0.026 g, 0.078 mmol) and C6D5Br
(0.5 mL) was added Mes2P(C6F4)B(C6F5)2 (0.060 g, 0.078 mmol)
dissolved in C6D5Br (0.5 mL). The mixture was shaken for 5 min and
transferred to an NMR tube for analysis. Quantitative formation of 10
was observed by NMR spectroscopy. After solvent removal under
vacuum, 10 was obtained as a cream colored solid in 81% yield
(70 mg). Crystals suitable for X-ray diffraction were grown by slowly
1
(s, Mes-p-CH3), 27.01 (d, JC−P = 14 Hz, P{C(CH3)3}2), 26.51
(d, JC−P = 5 Hz, P{C(CH3)3}2), 21.68 (s, Mes-o-CH3). 19F NMR
3
(CD2Cl2): δ 133.19 (d, 3JF−F = 23 Hz, 2F, o-C6F5), −135.10 (d, 3JF−F
=
3
23 Hz, 2F, o-C6F5), −164.13 (t, JF−F = 20 Hz, 1F, p-C6F5), −164.36
3
3
(t, JF−F = 20 Hz, 2F, p-C6F5), −167.56 (dd, JF−F = 20, 19 Hz, 2F,
m-C6F5), −167.84 (dd, 3JF−F = 20, 19 Hz, 2F, m-C6F5). 31P{1H} NMR
(CD2Cl2): δ 54.02 (s, PtBu2). UV−vis: λmax (ε)/nm 343 (1155). Anal.
Calcd for C102H106B2Cl2F30N4NiO2P2: C, 55.16; H, 4.85; N, 2.54;
Found: C, 52.78; H, 4.93; N, 1.95.
1
adding pentane to the above sample and letting stand 24 h. H NMR
(C6D5Br, −25 °C): 7.25−7.67 (br m, 4H, P(C6H2)2), 5.90 (br s,
1H, COD), 5.16 (br s, 1H, COD), 4.92 (br s, 2H, COD), 3.10
(br s, 3H, P(C6H2Me-4)), 2.88 (br s, 3H, P(C6H2Me-4)), 2.41−2.10
(br m, 18H, P(C6H2Me-2,6)2, COD), 1.54 (br s, 2H, COD), 1.25
Synthesis of [SIMesH][(p-cymene)RuCl2(Cy2PC6F4BF(C6F5)2)]
16, [SIMesH][(p-cymene)RuCl2(tBu2P(CH2)4OB(C6F5)3)] 17. These
compounds were prepared in a similar fashion and thus only one
preparation is detailed. A solution of [(p-cymene)RuCl2]2 (0.0753 g,
0.123 mmol) in CH2Cl2 (6 mL) was added to a solution of 6 (0.250 g,
0.246 mmol) in CH2Cl2 (9 mL) to give a clear, deep red solution. The
reaction mixture was stirred at room temperature overnight. The
resulting solution was concentrated under vacuum to approximately
1 mL. Fifteen milliliters of pentane were added to precipitate the
product. The orange powder was washed with a further 2 × 4 mL of
pentane and dried under vacuum.
(br m, 3H, BMe), 0.44 (br s, 3H, PtMe). 11B{1H} NMR (C6D5Br):
1
−14.60 (br). 13C{1H} NMR (C6D5Br) partial: 148.87 (dm, JC−F
=
1
250 Hz, CF), 145.10 (dm, JC−F = 250 Hz, CF), 142.50 (br, quat),
1
1
141.45 (dm, JC−F = 245 Hz, CF), 137.30 (dm, JC−F = 250 Hz, CF),
130.83 (s, p-C6H2), 111.68 (br, COD), 108.01 (m, COD), 30.03 (br,
COD), 29.37 (br, COD), 24.50 (br, C6H2Me-4), 20.94 (br, C6H2Me-
2,6), 11.33 (br, BMe), 5.39 (br, PtMe). 19F NMR (C6D5Br): −128.70
(m, 3JF−F = 20 Hz, 1F, C6F4), −129.28 (m, 1F, C6F4), −130.04 (m, 1F,
3
3
C6F4), −132.21 (m, JF−F = 22 Hz, 1F, C6F4), −132.57 (m, JF−F
=
24 Hz, 4F, o-C6F5), −163.81 (m, 3JF−F = 21 Hz, 2F, p-C6F5), - 166.65
16. Orange powder. Yield 300 mg (92%). Crystals suitable for X-ray
diffraction were grown from slow diffusion of pentane into a concen-
(m, JF−F = 22 Hz, 4F, m-C6F5). 31P{1H} NMR (C6D5Br): −11.33
3
1
1
(d, JP−Pt = 3831 Hz, P(Mes)2). Anal. Calcd for C46H40BF14PPt: C,
trated CH2Cl2 solution. H NMR (CD2Cl2): 8.63 (s, 1H, NCHN),
7.05 (s, 4H, m-MesAr-H), 4.98 (d, 3JH−H = 6 Hz, 2H, p-cymene C6H4),
50.43; H, 3.68; Found: C, 50.27; H, 3.41.
3
Synthesis of [SIMesH][tBu2P(CH2)4OB(C6F5)3] 13. To a solution
of tBu2PH(CH2)4OB(C6F5)3 (0.500 g, 0.685 mmol) in toluene
(5 mL) a solution of SIMes (0.2157 g, 0.685 mmol) in toluene (3 mL)
was added. The resulting clear, yellow solution was stirred at room
temperature for 1 h. All volatiles were removed via vacuum. The
yellow oil was washed with 4 × 5 mL of pentane and dried under
vacuum. The final product was a white powder. Yield 682 mg (96%).
1H NMR (CD2Cl2): 7.96 (s, 1H, NCHN), 7.06 (s, 4H, m-MesAr-H),
4.44 (s, 4H, NCH2CH2N), 3.43 (br m, 2H, CH2CH2O), 2.34 (s, 12H,
Mes-o-CH3), 2.33 (s, 6H, Mes-p-CH3), 1.53 (br m, 2H, CH2CH2OB),
1.46 (br m, 2H, PCH2CH2), 1.26 (br m, 2H, PCH2CH2), 1.03 (d,
4.58 (d, JH−H = 6 Hz, 2H, p-cymene C6H4), 4.40 (s, 4H,
NCH2CH2N), 2.81 (br s, 2H, P{C6H11}2), 2.46 (septet, 1H, JH−H
3
=
7 Hz, p-cymene CH{CH3}2), 2.38 (s, 12H, Mes-o-CH3), 2.32 (s, 6H,
Mes-p-CH3), 2.28−1.12 (br m, 20H, P{C6H11}2), 1.83 (s, 3H,
3
p-cymene-p-CH3), 1.00 (d, JH−H = 7 Hz, 6H, p-cymene CH{CH3}2).
11B NMR (CD2Cl2): −0.52 (br). 13C{1H} NMR (CD2Cl2) partial:
160.76 (s, NCHN), 141.68 (s, ipso-MesAr−C-N), 135.45 (s, o-MesAr−
C), 130.58 (s, m-MesAr−C), 130.43 (s, p-MesAr−C), 108.03 (s, p-
cymene C6H4), 94.63 (br s, p-cymene C6H4), 85.84 (br s, p-cymene
C6H4), 30.80 (s, p-cymene CH{CH3}2), 29.79 (s, P{C6H11}2), 28.65
(d, JC−P = 11 Hz, P{C6H11}2), 28.02 (d, JC−P = 13 Hz, P{C6H11}2),
4714
dx.doi.org/10.1021/ic2026895 | Inorg. Chem. 2012, 51, 4711−4721

Inorganic Chemistry
Article
Table 1. Crystallographic Parameters
1
6
10
11
12
16
formula
FW
C84H83BF15P3Pt
1676.31
C84H100B2Cl2F30NiP4
1954.75
C40H37BF15N2P
872.50
monoclinic
P21/c
C46H40BF14PPt
1095.65
C66H57BF15OP3Pt
1449.93
C61H63BCl2F15N2PRu
1322.88
cryst. system
space group
a (Å)
triclinic
triclinic
monoclinic
P21/n
triclinic
triclinic
P1
P1
̅
P1
̅
P1
̅
̅
13.6554(8)
17.3383(10)
17.5183(11)
75.178(3)
67.214(3)
82.180(3)
3693.5(4)
2
11.6221(6)
13.0066(7)
16.1921(9)
89.881(2)
81.754(2)
66.233(2)
2212.7(2)
1
13.5325(14)
12.9076(13)
23.869(3)
90
9.031(5)
14.3247(11)
14.9512(12)
16.0283(13)
86.229(4)
64.236(4)
87.839(4)
3084.7(4)
2
11.7251(9)
12.7188(10)
20.8837(16)
106.730(4)
102.730(4)
90.302(4)
2901.4(4)
2
b (Å)
19.620(11)
23.802(13)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z
99.999(1)
90
95.685(9)
4106.0(7)
4
4197(4)
4
dcalc (g cm−3
μ (mm−1
)
1.507
1.467
1.411
1.734
3.478
39136
0.1113
3726
1.561
1.514
)
2.048
0.459
0.167
2.440
0.480
total data
94061
37124
38674
47708
42750
Rint
0.0336
0.0512
0.0254
5071
0.0465
0.0724
2
2
Fo > 2σ(Fo )
parameters
R1
24500
6542
11929
6843
941
560
546
558
788
748
0.0282
0.0520
0.0548
0.1422
1.045
0.0855
0.2591
1.076
0.0379
0.0495
wR2
0.0697
0.1308
0.0948
0.1225
GOF
1.028
1.007
1.022
1.008
26.77 (s, P{C6H11}2), 21.91 (br m, P{C6H11}2), 21.68 (s, Mes-p-CH3),
21.20 (s, p-cymene CH{CH3}2), 18.28 (s, Mes-o-CH3), 17.51 (s,
p-cymene-p-CH3). 19F NMR (CD2Cl2): −130.76 (br s, 2F, C6F4),
−133.86 (br m, 2F, C6F4), −136.51 (br m, 4F, o-C6F5), −163.23
(t, 3JF−F = 20 Hz, 2F, p-C6F5), −167.70 (m, 4F, m-C6F5), −192.52 (br
s, 1F, B-F). 31P{1H} NMR (CD2Cl2): δ 37.55 (br s, PCy2). Anal. Calcd
for C61H63BCl2F15N2PRu: C, 55.38; H, 4.80; N, 2.12 Found: C,
53.48;18 H, 4.87; N, 2.28.
heavy atom positions were determined using direct methods employ-
ing the SHELXTL direct methods routine. The remaining non-
hydrogen atoms were located from successive difference Fourier map
calculations. The refinements were carried out by using full-matrix
least-squares techniques on F, minimizing the function σ (Fo − Fc)2,
2
2
where the weight σ is defined as 4Fo /2σ (Fo ) and Fo and Fc are the
observed and calculated structure factor amplitudes, respectively. In
the final cycles of each refinement, all non-hydrogen atoms were
assigned anisotropic temperature factors in the absence of disorder or
insufficient data. In the latter cases, atoms were treated isotropically.
C−H atom positions were calculated and allowed to ride on the
carbon to which they were bonded, assuming a C−H bond length of
0.95 Å. H-atom temperature factors were fixed at 1.10 times the
isotropic temperature factor of the C atom to which they were bonded.
The H-atom contributions were calculated, but not refined. The
locations of the largest peaks in the final difference Fourier map
calculation as well as the magnitude of the residual electron densities
in each case were of no chemical significance. Additional details are
provided in the Supporting Information.
17. Orange powder. Yield 282 mg (87%). 1H NMR (CD2Cl2): 9.42
(s, 1H, NCHN), 7.03 (s, 4H, m-MesAr-H), 5.00 (br s, 4H, p-cymene,
C6H4), 4.34 (s, 4H, NCH2CH2N), 3.12 (br m, 4H, CH2CH2O), 2.62
(septet, 3JH−H = 7 Hz, 1H, p-cymene CH{CH3}2), 2.41 (s, 12H, Mes-
o-CH3), 2.32 (s, 6H, Mes-p-CH3), 2.08 (br s, 4H, CH2CH2OB), 1.94
(br s, 4H, PCH2CH2), 1.78 (s, 3H, p-cymene p-CH3), 1.52 (br m, 4H,
3
PCH2CH2), 1.13 (d, JH−H = 7 Hz, 6H, p-cymene CH{CH3}2), 1.09
3
(d, JH−P = 13 Hz, 18H, P{C(CH3)3}2). 11B NMR (CD2Cl2): −2.93
(s). 13C{1H} NMR (CD2Cl2) partial: 161.57 (s, NCHN), 141.39
(s, ipso-MesAr−C-N), 135.77 (s, o-MesAr−C), 130.72 (s, m-MesAr−
C), 130.37 (s, p-MesAr−C), 103.93 (s, p-cymene C6H4), 94.29 (s,
p-cymene C6H4), 87.99 (br s, p-cymene C6H4), 87.03 (br s, p-cymene
C6H4), 63.21 (br s, CH2CH2O), 51.60 (s, NCH2CH2N), 38.01 (d,
RESULTS AND DISCUSSION
■
1
1JC−P = 12 Hz, P{C(CH3)3}2), 36.07 (d, JC−P = 10 Hz, PCH2CH2),
The species Cy2PHC6F4BF(C6F5)2 reacts with Pt(PPh3)4 to
yield the new product 1 which was isolated in 86% yield. The
11B resonance of 1 was observed at −0.78 ppm. The
corresponding 19F NMR signals at −130.41 and −132.83
ppm were attributable to the C6F4 fragment while the
resonances at −135.38, −162.35, and −166.81 ppm arose
from the C6F5 groups. Retention of the borate portion of
the phosphonium-borate was reasoned because of the unique
resonance at −192.65 ppm, attributable to a B-F unit. The
31P{1H} NMR spectrum of 1 showed three doublet of doublets
at 28.98, 22.01, and 18.16 ppm with P−P coupling constants of
341, 19, and 20 Hz. These signals also exhibit Pt satellites with
Pt−P coupling constants of 2805, 2290, and 2779 Hz,
respectively. These spectral features exhibited some degree of
second order character and thus the above coupling constant
and chemical shift data were derived from an iterative process
of spectral simulation (Figure 1). The 31P{1H} NMR data are
consistent with the coordination of three chemically
inequivalent phosphorus centers to Pt, inferring that two
3
30.93 (d, JC−P = 3 Hz, P{C(CH3)3}2), 29.09 (s, CH2CH2O), 23.70
3
(d, JC−P = 3 Hz, PCH2CH2), 30.25 (s, p-cymene CH{CH3}2), 21.95
(s, p-cymene CH{CH3}2), 21.13 (s, Mes-p-CH3), 18.20 (s, Mes-o-
CH3), 17.14 (s, p-cymene-p-CH3). 19F NMR (CD2Cl2): −134.61
(d, 3JF−F = 23 Hz, 4F o-C6F5), −165.01 (t, 3JF−F = 20 Hz, 2F, p-C6F5),
−168.24 (br m, 4F, m-C6F5). 31P{1H} NMR (CD2Cl2): δ 41.54
(s, PtBu2). Anal. Calcd for C61H67BCl2F15N2OPRu: C, 54.56; H, 5.03;
N, 2.09; Found: C, 55.16; H, 5.40; N, 2.59.
X-ray Data Collection and Reduction. Crystals were coated in
Paratone-N oil in the glovebox, mounted on a MiTeGen Micromount
and placed under a N2 stream, thus maintaining a dry, O2-free
environment for each crystal. The data for crystals of 10 were collected
on a Nonius Kappa-CCD diffractometer; for crystals of 4, 6, 7, and 8,
data were collected on a Bruker Apex II diffractometer (Table 1). The
data were collected at 150(2) K for all crystals. The frames were
integrated with the Bruker SAINT software package using a narrow-
frame algorithm. Data were corrected for absorption effects using the
empirical multiscan method (SADABS).
Structure Solution and Refinement. Non-hydrogen atomic
scattering factors were taken from the literature tabulations.47 The
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Figure 1. (a) Simulated and (b) experimental 31P{1H} NMR spectra
for 1.
PPh3 units remain bound to Pt, but are in distinct environ-
ments. The 1H NMR spectrum of 1 shows the expected
resonances due to the phenyl and cyclohexyl groups consistent
with a ratio of the PPh3/phosphine-borate of 2:1. In addition, a
doublet of doublet of doublets is seen at −6.73 ppm with P−H
couplings of 160, 17, and 13 Hz, typical of a Pt-hydride in a
P3PtH square planar coordination sphere.27 As well, this signal
exhibits Pt satellites with a Pt−H coupling of 778 Hz (Figure 2).
Figure 3. Pov-ray depictions of 1; C, black; P, orange; F, pink; Pt,
light-wood; B, yellow-green; H, gray.
The corresponding cis-P−Pt−P angles are 105.741(15)° and
98.138(16)°, while the cis-P−Pt−H angles are 77.9(10)° and
78.5(10)°. These distortions of the coordination sphere toward
the hydride are not unexpected due to the steric demands of
the phosphine ligands about the formally cationic Pt center.
The corresponding reaction of tBu2PHC6F4BF(C6F5)2 with
Pt(PPh3)4 afforded a product 2 in 78% yield. In contrast to 1,
this species exhibits 11B, 31P, and 19F NMR spectra consistent
with the presence of the anion [(tBu2PC6F4BF(C6F5)2)] (10,
vide infra). In addition, the overlapping 31P{1H} NMR triplet
and doublet resonances at 23.14 and 22.90 ppm with a P−P
coupling of 19 Hz and Pt−P couplings of 2220 and 2819 Hz
were observed. Together with the 1H NMR doublet of doublet
of doublets at −5.76 ppm, these data are consistent with the
formulation of 2 as [(PPh3)3PtH][(tBu2PC6F4BF(C6F5)2)]
(Scheme 3). The inability of the anion to displace PPh3, in this
case, is attributed to steric issues.
While modification of the phosphonium borate results in
altered reactivity, the reaction of Cy2PHC6F4BF(C6F5)2 with
Pd(PPh3)4 affords the Pd analogue of 1, namely cis-(PPh3)2-
PdH(Cy2PC6F4BF(C6F5)2) 3, in 64% isolated yield (Scheme 3).
The 11B, 19F, and 31P NMR spectral parameters are analogous to
those of 1. The 1H NMR spectrum of 3 was similar to that of 1,
exhibiting the characteristic hydride resonance at −8.05 ppm. It is
also noteworthy that a small portion of an additional hydride
complex is formed in the reaction affording 3. The hydride signal
for this species is slightly upfield from 3. Although this species
could not be isolated, it is proposed that the additional product is
the isomer in which the hydride is trans to the phosphine-borate.
Attempts to extend this oxidative addition approach to yield Ni-
hydride complexes via reaction of the phosphonium borate with
Ni(PPh3)4 led only to an inseparable mixture of products.
An alternative strategy to the reaction of the phosphonium
borate with transition metal precursors involves initial deproto-
nation. Deprotonation of Cy2PHC6F4BF(C6F5)2 with tBu3P
proceeds as the latter phosphine is more basic than the P center
in the phosphonium-borate. This afforded ready access to
[tBu3PH][Cy2PC6F4BF(C6F5)2] 4 in 93% isolated yield as a
white powder (Scheme 3). The 1H NMR spectrum of 4
confirms the protonation of the tBu3P as evidenced by the
1
Figure 2. Hydride resonance observed in H NMR spectrum of 1.
The data is consistent with the formulation of 1 as cis-(PPh3)2-
PtH(Cy2PC6F4BF(C6F5)2), but stands in contrast to those
previously reported for cations of the form [(R3P)3MH]+ (M =
Ni, Pd) which are reported to be stereochemically nonrigid.28
Thus it can be inferred that oxidative addition of the P−H bond
of the phosphonium borate occurs resulting in the cis-
disposition of the Pt-hydride and the coordinated PCy2
fragment of the phosphine-borate.
The formulation of 1 was confirmed via a crystallographic
study (Figure 3), affirming the anticipated pseudosquare planar
coordination geometry about Pt with a cis-disposition of the
Pt-hydride and the coordinated phosphine-borate. The Pt−P
distances for phosphine-borate and the PPh3 groups cis and
trans to the hydride were found to be 2.3188(4) Å, 2.3195(5) Å,
and 2.3460(5) Å, respectively. The longest of these Pt−P
distances is consistent with the strong trans influence of the
hydride. The refined Pt−H distance was determined to be
1.71(3) Å. The coordination sphere of Pt is distorted from that
of an ideal square plane as the trans-P−Pt−P angle is
156.047(16)°, while the trans-P−Pt−H angle is 174.1(11)°.
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Scheme 3. Synthesis of Complexes 1−10
Figure 4. Pov-ray depiction of anion of 6; C, black; P, orange; F, pink;
Ni, light-blue; B, yellow-green.
doublet at 6.09 ppm with a P−H coupling constant of 472 Hz.
Furthermore, the 31P{1H} resonances at 48.99 ppm and
−10.37 ppm are attributable to the phosphonium cation [tBu3PH]
and the PCy2 fragment, respectively. The 11B and 19F signals
exhibit only minor changes as a result of this deprotonation. In
a completely analogous fashion this deprotonation can be
accomplished by employing the N-heterocyclic carbene, SIMes
affording the corresponding salt [SIMesH][Cy2PC6F4BF-
(C6F5)2] 5 in 92% isolated yield. Subsequent reaction of 4 or
5 with NiCl2(DME) yielded the pink powders 6 and 7 in 73
and 75% yield, respectively. The 11B and 19F NMR spectra of
these products are only slightly perturbed from those of the
precursor salts. The 31P{1H} NMR of 6 shows signals at 56.33
and 10.17 ppm in a 1:1 ratio consistent with two phosphonium
cations and two phosphines bound to Ni. The corresponding
salt 7 showed only a single 31P{1H} resonance at 10.60 ppm.
These data suggest the formulations of 6 and 7 as [Base-
H]2[trans-Cl2Ni(Cy2PC6F4BF(C6F5)2)2] (Base = tBu3P 6,
SIMes 7) (Scheme 3). In the case of 6, this formulation was
confirmed crystallographically (Figure 4). The dianionic nature
of nickel center in 6 results from the two coordinated chlorine
atoms and the two pendant borate centers on the coordinated
phosphines. The Ni center sits on a crystallographic 2-fold with
Ni−Cl and Ni−P distances of 2.1672(7) Å and 2.2292(7) Å,
respectively. The Ni coordination sphere is essentially square
planar as the Cl−Ni−P angles are 90.54(3)° and 89.46(3)°,
while the Cl−Ni−Cl and P−Ni−P angles are 180.0° and
179.999(1)°, respectively. The UV−vis spectra for both 6 and 7
show a single absorption peak at 382 nm with a molar
absorptivity coefficient of 6096 and 8525 L mol−1 cm−1,
respectively.
The corresponding reactions of 4 or 5 with PdCl2(PhCN)2
provide facile access to the analogous salts [BaseH]2[trans-
Cl2Pd(Cy2PC6F4BF(C6F5)2)2] (Base = tBu3P 8, SIMes 9)
which were isolated as pale yellow powders in 81% and 47%
yields, respectively (Scheme 3). These products exhibit NMR
parameters analogous to 6 and 7. Efforts to extend the
chemistry to salts of [tBu2PC6F4BF(C6F5)2] were undertaken
with the isolation of [C10H6N2(Me)4H][tBu2PC6F4BF(C6F5)2]
10 (Scheme 3), as well as with the analogous phosphonium and
imidazolium salts. The spectroscopic and crystallographic data
(Figure 5) confirmed the formulation of 10. Nonetheless,
combination of 10 and NiCl2(DME) led to no reaction,
presumably a result of the additional steric demands of this
derivative.
A third strategy for formation of a metal complex of anionic
phosphine-borate derivatives was demonstrated in the reaction
of (COD)PtMe2 with the neutral phosphine-borane
Mes2PC6F4B(C6F5)2. The combination of these species results
in an immediate reactions affording the new species 11 which
was isolated in 81% yield as a cream colored solid. The 11B{1H}
NMR spectrum of 11 shows a peak at −14.60 ppm, consistent
1
with the formation of a methyl-borate center. The H NMR
spectrum suggests a dissymmetric environment for the
coordinated COD. In addition methyl resonances at 1.25 and
0.44 ppm are attributable to the boron-bound and Pt-bound
methyl groups. The corresponding 13C{1H} NMR resonances
for these methyl groups are seen at 11.33 and 5.39 ppm,
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Figure 6. Pov-ray depiction of 11; C, black; P, orange; F, pink; Pt,
light-wood; B, yellow-green.
addition of the P−H bond to Pt affording the species, cis-
(PPh3)2PtH(tBu2P(CH2)4OB(C6F5)3) 12 in 84% yield
(Scheme 5). This species is characterized by a 11B NMR
Figure 5. Pov-ray depiction of 10; C, black; P, orange; F, pink; N,
light-blue; B, yellow-green; H, gray.
respectively. The 19F NMR resonances are as expected, with a
gap between the signals for the meta and para fluorines of the
C6F5 groups of 2.9 ppm, indicative of formation of a methyl
borate. The presence of four separate resonances for the
fluorines of the C6F4 bridge indicate restricted rotation about
the P−C6F4 bond not seen in the starting phosphine-borane or
previously discussed phosphine borate complexes. The 31P{1H}
NMR spectrum consists of a single resonance at −11.33 ppm,
which exhibits Pt-satellites and a Pt−P coupling constant of
3831 Hz. Based upon these data, 11 is best formulated as
(COD)PtMe(Mes2PC6F4BMe(C6F5)2) (Scheme 4). The solid
Scheme 5. Synthesis of 12−15
Scheme 4. Synthesis of Complex 11
state structure of 11 was determined by X-ray crystallography
(Figure 6) confirming the zwitterionic nature resulting from the
pendant methyl borate anion and the phosphine-stabilized
cationic platinum center. The geometry about platinum is
distorted square planar. The Pt−P bond length of 2.348(4) Å is
typical for related phosphorus−platinum complexes.29 Interest-
ingly, addition of a second equivalent of the phosphino-borane
did not result in a second methyl abstraction or displacement of
the cycloctadiene ligand. The formation of 11 demonstrates the
ability of the present phosphino-boranes to act as an ambiphilic
ligands effecting methyl abstraction and subsequent coordina-
tion of the phosphine to the resulting vacant coordination site.
This reactivity is reminiscent of the reactions of Ni-methyl
derivatives with phosphinoethylboranes described by Tilley et al.11
This approach to anionic-phosphine-ligand complexes can be
extended to other products derived from FLP chemistry. For
example, the product of THF ring-opening tBu2PH(CH2)4OB-
(C6F5)3) reacts with Pt(PPh3)4 resulting in the oxidative
resonance at −2.94 ppm and 19F NMR signals typical of an
anionic borate. The 31P{1H} NMR data for 12 shows multiplets
at 56.56, 21.57, and 18.06 ppm consistent with coordination of
the anionic phosphine to a square planar Pt with two PPh3
ligands. The most diagnostic peak in the 1H NMR spectrum of
12 is the resonance attributable to the hydride which is seen as
a multiplet at −6.92 ppm with P−H couplings of 162 and
14 Hz. It is noteworthy that this resonance is close to that
described above for 1. This signal also exhibits Pt-satellites with
a Pt−H coupling of 786 Hz (Figure 7). The formulation of 12
was also confirmed crystallographically (Figure 8). The geo-
metry about Pt in 12 is very similar to that seen in 1. The Pt−P
distances in 12 for the phosphine-borate, and the PPh3 groups
that are cis and trans to the hydride are 2.3142(9) Å, 2.3208(9) Å,
and 2.3543(10) Å, respectively. The shortest of these Pt−P
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a maximum absorption at 343 nm, blue-shifted compared to 6
and 7 due to the greater donor ability of this phosphine borate
ligand. The molar absorptivity coefficient is 1155 L mol−1 cm−1.
Finally, reaction of 7 and 13 with [(p-cymene)RuCl2]2
proceeds to give the new orange products 16 and 17 in 92
and 87% isolated yield, respectively. These species show the 11
B
and 19F NMR spectra characteristic of the coordination of the
respective anion phosphine-borates as well as 31P NMR
resonances at 37.55 and 41.54 ppm respectively. The 1H
spectra are as expected with resonances attributable to the
p-cymene, cyclohexyl, and imidiazolium protons. These data
support the formulation of 16 and 17 as [SIMesH][(p-
cymene)RuCl2(Cy2PC6F4BF(C6F5)2)] and [SIMesH][(p-
cymene)RuCl2(tBu2P(CH2)4OB(C6F5)3)], respectively
(Scheme 6). These formulations were further validated by the
1
Scheme 6. Synthesis of 16−17
Figure 7. Hydride resonance observed in H NMR spectrum of 12.
Figure 8. Pov-ray depiction of 12; C, black; P, orange; F, pink; Pt,
light-wood; B, yellow-green; H, gray.
bond length results from the phosphine-borate consistent with
the greater donor ability of the trialkylphosphine center of this
anionic moiety. The distortions from square planarity are
similar to those in 1 with trans-P−Pt−P angle of 156.88(4)°
and cis-P−Pt−P angles of 105.62(3)° and 97.49(3)°.
In contrast to the fluoro-arene phosphonium borate,
tBu2PH(CH2)4OB(C6F5)3 could not be deprotonated with
PtBu3 or proton sponge. This is consistent with the great
basicity of the P center in tBu2PH(CH2)4OB(C6F5)3. None-
theless, the phosphonium borate tBu2PH(CH2)4OB(C6F5)3 is
readily deprotonated via reaction with SIMes. In this fashion,
[SIMesH][tBu2P(CH2)4OB(C6F5)3] 13 was prepared in 96%
isolated yield (Scheme 5). In a fashion analogous to that
employed to prepare 7 and 9, subsequent reaction with
NiCl2(DME) and PdCl2(PhCN)2 afforded the analogous
complexes [SIMesH]2[trans-Cl2Ni(tBu2PC4H8OB(C6F5)3)2]
14 and [SIMesH]2[trans-PdCl2(tBu2P(CH2)4OB(C6F5)3)2]
15, respectively (Scheme 5). These products were isolated as
blue and yellow powders, respectively, in yields of 72 and 47%.
The 31P{1H} NMR spectral data for 14 and 15 were analogous
to those of 7 and 9, respectively, with the characteristic
resonances at 54.02 and 40.61 ppm, respectively. The 11B and
19F NMR spectra for 15 indicate that both phosphine borates
coordinated to Pd are chemically equivalent. However, 14
exhibits two 11B resonances at −2.41 and −2.93 ppm in a 1:1
ratio. Also, the presence of six multiplets in the 19F NMR
spectrum corresponding to two sets of inequivalent C6F5
groups, suggests that inhibited rotation about P−Ni bonds
affords two rotomers of this species. This blue complex exhibits
X-ray crystallographic study of 16 (Figure 9). The Ru adopts a
pseudotetrahedral, “piano-stool” type geometry with a η6-bound
Figure 9. Pov-ray depiction of anion of 16; C, black; P, orange; F,
pink; Cl, green; Ru, light-green; B, yellow-green.
p-cymene acting as the “seat” of the stool. The “legs” of the
stool are derived from the Ru−P and two Ru−Cl bonds which
were found to be 2.3996(11) Å, 2.4076(12) Å, and 2.4172(12) Å,
respectively. The nature of 16 is similar to that seen for
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(6) (a) Joo, F.; Toth, Z. J. Mol. Catal. 1980, 8, 369. (b) Pierre Genet,
J.; Savignac, M. J. Organomet. Chem. 1999, 576, 305.
(7) Hoic, D. A.; Davis, W. M.; Fu, G. C. J. Am. Chem. Soc. 1996, 118,
(p-cymene)RuCl2(Ph2PCH2CH2(9-BBN)] reported by Bourissou
and co-workers.10a
8176.
CONCLUSIONS
■
(8) Jaska, C. A.; Dorn, H.; Lough, A. J.; Manners, I. Chem.Eur. J.
2003, 9, 271.
Herein we have demonstrated the utility of the phosphonium
borates derived from FLP chemistry in the formation of
zwitterionic phosphine complexes. These observations illustrate
that FLP chemistry offers convenient access to unique anionic
phosphine ligands that can be employed with a variety of
transition metal precursors. While this aspect has not been the
primary target of FLP chemistry, the present report suggests
that FLP chemistry provides a unique and facile strategy for the
ligand design and synthesis of anionic phosphines. To this end
we are exploring the potential of such ligands complexes in
applications in catalysis.
(9) (a) Thomas, J. C.; Peters, J. C. Polyhedron 2004, 23, 489.
(b) Thomas, J. C.; Peters, J. C. Polyhedron 2004, 23, 2901. (c) Thomas,
J. C.; Peters, J. C. Inorg. Chem. 2003, 42, 5055. (d) Thomas, C. M.;
Peters, J. C. Inorg. Chem. 2004, 43, 8. (e) Thomas, J. C.; Peters, J. C.
Inorg. Chem. 2004, 43, 8. (f) Saouma, C. T.; Muller, P.; Peters, J. C.
J. Am. Chem. Soc. 2009, 131, 10358. (g) Mehn, M. P.; Brown, S. D.;
Paine, T. K.; Brennessel, W. W.; Cramer, C. J.; Peters, J. C.; Que, L. Jr.
Dalton Trans. 2006, 1347. (h) Mankad, N. P.; Peters, J. C. Chem.
Commun. 2008, 1061. (i) Mankad, N. P.; Antholine, W. E.; Szilagyi, R.
K.; Peters, J. C. J. Am. Chem. Soc. 2009, 131, 3878. (j) Mankad, N. P.;
Peters, J. C. Chem. Commun. 2008, 1061. (k) MacBeth, C. E.; Thomas,
J. C.; Betley, T. A.; Peters, J. C. Inorg. Chem. 2004, 43, 4645.
(l) MacBeth, C. E.; Thomas, J. C.; Betley, T. A.; Peters, J. C. Inorg.
Chem. 2004, 43, 4645. (m) Lu Connie, C.; Peters, J. C. Inorg. Chem.
2006, 45, 8597. (n) Lu, C. C.; Peters, J. C. Inorg. Chem. 2006, 45,
8597. (o) Lu, C. C.; Peters, J. C. J. Am. Chem. Soc. 2004, 126, 15818.
(p) Jenkins David, M.; Peters, J. C. J. Am. Chem. Soc. 2005, 127, 7148.
(q) Feldman, J. D.; Peters, J. C.; Tilley, T. D. Organometallics 2002, 21,
4050. (r) Brown, S. D.; Mehn, M. P.; Peters, J. C. J. Am. Chem. Soc.
2005, 127, 13146. (s) Betley, T. A.; Peters, J. C. Inorg. Chem. 2003, 42,
5074. (t) Betley, T. A.; Peters, J. C. Inorg. Chem. 2002, 41, 6541.
(u) Betley, T. A.; Peters, J. C. Inorg. Chem. 2003, 42, 5074.
(10) (a) Vergnaud, J.; Grellier, M.; Bouhadir, G.; Vendier, L.; Sabo-
Etienne, S.; Bourissou, D. Organometallics 2008, 27, 1140. (b) Fontaine,
F. G.; Boudreau, J.; Thibault, M. H. Eur. J. Inorg. Chem. 2008, 5439.
(c) Bouhadir, G.; Amgoune, A.; Bourissou, D. Adv. Organomet. Chem.
2010, 58, 1. (d) Oakley, S. R.; Parker, K. D.; Emslie, D. J. H.;
Vargas-Baca, I.; Robertson, C. M.; Harrington, L. E.; Britten, J. F.
Organometallics 2006, 25, 5835. (e) Kolpin, K. B.; Emslie, D. J. H.
Angew. Chem., Int. Ed. 2010, 49, 2716. (f) Emslie, D. J. H.; Harrington,
L. E.; Jenkins, H. A.; Robertson, C. M.; Britten, J. F. Organometallics
2008, 27, 5317. (g) Emslie, D. J. H.; Blackwell, J. M.; Britten, J. F.;
Harrington, L. E. Organometallics 2006, 25, 2412. (h) Bontemps, S.;
Bouhadir, G.; Miqueu, K.; Bourissou, D. J. Am. Chem. Soc. 2006, 128,
12056. (i) Bontemps, S.; Bouhadir, G.; Apperley, D. C.; Dyer, P. W.;
Miqueu, K.; Bourissou, D. Chem.Asian J. 2009, 4, 428.
ASSOCIATED CONTENT
* Supporting Information
Crystallographic information files (CIF). This material is
available free of charge via the Internet at http://pubs.acs.org.
■
S
AUTHOR INFORMATION
Corresponding Author
*E-mail: dstephan@chem.utoronto.ca.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The support of LANXESS Inc, NSERC of Canada and the
Ontario Centres of Excellence is gratefully acknowledged.
D.W.S. is grateful for the award of a Canada Research Chair
and a Killam Research Fellowship. S.L.G. is grateful for the
award of an NSERC postgraduate scholarship.
REFERENCES
■
(1) (a) Karsch, H. H.; Appelt, A.; Mueller, G. J. Chem. Soc., Chem.
Commun. 1984, 1415. (b) Karsch, H. H.; Appelt, A.; Mueller, G.
Organometallics 1985, 4, 1624. (c) Karsch, H. H. Phosphorus, Sulfur
Silicon Relat. Elem. 1993, 77, 41. (d) Mueller, G.; Lachmann, J. Z.
Naturforsch., B: Chem. Sci. 1993, 48, 1248. (e) Demonceau, A.; Simal,
F.; Noels, A. F.; Vinas, C.; Nunez, R.; Teixidor, F. Tetrahedron Lett.
1997, 38, 4079. (f) Chen, L.; Yu, G.-A.; Li, F.; Zhu, X.; Zhang, B.;
Guo, R.; Li, X.; Yang, Q.; Jin, S.; Liu, C.; Liu, S.-H. J. Organomet. Chem.
2010, 695, 1768.
(2) (a) Knapp, V.; Muller, G. Angew. Chem., Int. Ed. 2001, 40, 183.
(b) Chandrasekaran, A.; Day Roberta, O.; Holmes Robert, R. Inorg.
Chem. 2002, 41, 1645. (c) Creutz, S. E.; Krummenacher, I.; Clough, C.
R.; Cummins, C. C. Chem. Sci. 2011, 2, 2166.
(3) (a) Hedden, D.; Roundhill, D. M. Inorg. Chem. 1985, 24, 4152.
(b) Hedden, D.; Roundhill, D. M. Inorg. Chem. 1986, 25, 9.
(c) Hedden, D.; Roundhill, D. M. Inorg. Synth. 1990, 27, 322.
(d) Hedden, D.; Roundhill, D. M.; Fultz, W. C.; Rheingold, A. L.
Organometallics 1986, 5, 336. (e) Park, S.; Hedden, D.; Rheingold, A.
L.; Roundhill, D. M. Organometallics 1986, 5, 1305.
(4) (a) Anselment Timo, M. J.; Anderson Carly, E.; Rieger, B.;
Boeddinghaus, M. B.; Faessler, T. F. Dalton Trans. 2011, 40, 8304.
(b) Anselment, T. M. J.; Anderson, C. E.; Rieger, B.; Boeddinghaus,
M. B.; Faessler, T. F. Dalton Trans. 2011, 40, 8304.
(11) Fischbach, A.; Bazinet, P. R.; Waterman, R.; Tilley, T. D.
Organometallics 2008, 27, 1135.
(12) (a) Gott, A. L.; Piers, W. E.; Dutton, J. L.; McDonald, R.;
Parvez, M. Organometallics 2011, 30 (16), 4236. (b) Kim, Y.; Jordan,
R. F. Organometallics 2011, 30 (16), 4250.
(13) Dureen, M. A.; Lough, A.; Gilbert, T. M.; Stephan, D. W. Chem.
Commun. 2008, 4303.
(14) Dureen, M. A.; Welch, G. C.; Gilbert, T. M.; Stephan, D. W.
Inorg. Chem. 2009, 48, 9910.
(15) (a) Momming, C. M.; Otten, E.; Kehr, G.; Frohlich, R.;
Grimme, S.; Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2009, 48,
6643. (b) Men
1796. (c) Men
accepted for publication. (d) Zhao, X. X.; Stephan, D. W. Chem.
Commun. 2011, 47, 1833. (e) Peuser, I.; Neu, R. C.; Zhao, X.; Ulrich,
M.; Schirmer, B.; Kehr, G.; Frohlich, R.; Grimme, S.; Erker, G.;
̈
̈
́
ard, G.; Stephan, D. W. J. Am. Chem. Soc. 2010, 132,
ard, G.; Stephan, D. W. Angew. Chem., Int. Ed. 2011,
́
̈
Stephan, D. W. Chem.Eur. J. 2011, asap.
(16) (a) McCahill, J. S. J.; Welch, G. C.; Stephan, D. W. Angew.
Chem., Int. Ed. 2007, 46, 4968. (b) Sortais, J. B.; Voss, T.; Kehr, G.;
Frohlich, R.; Erker, G. Chem. Commun. 2009, 7417. (c) Momming, C.
M.; Kehr, G.; Frohlich, R.; Erker, G. Chem. Commun. 2011, 47, 2006.
(17) Ullrich, M.; Seto, K. S. H.; Lough, A. J.; Stephan, D. W. Chem.
Commun. 2009, 2335.
(18) (a) Dureen, M. A.; Stephan, D. W. Organometallics 2010, 29,
6594. (b) Dureen, M. A.; Brown, C. C.; Stephan, D. W.
Organometallics 2010, 29, 6422. (c) Dureen, M. A.; Stephan, D. W.
̈
(5) (a) White, G. S.; Stephan, D. W. Organometallics 1988, 7, 903.
(b) Seewald, P. A.; White, G. S.; Stephan, D. W. Can. J. Chem. 1988,
66, 1147. (c) White, G. S.; Stephan, D. W. Organometallics 1987, 6,
2169. (d) White, G. S.; Stephan, D. W. Inorg. Chem. 1985, 24, 1499.
(e) Stephan, D. W. Inorg. Chem. 1984, 23, 2207. (f) Suzuki, T.;
Morikawa, A.; Kashiwabara, K. Bull. Chem. Soc. Jpn. 1996, 69, 2539.
(g) Chu, W.-C.; Wu, C.-C.; Hsu, H.-F. Inorg. Chem. 2006, 45, 3164.
̈
J. Am. Chem. Soc. 2009, 131, 8396. (d) Momming, C. M.; Fromel, S.;
̈
4720
dx.doi.org/10.1021/ic2026895 | Inorg. Chem. 2012, 51, 4711−4721

Inorganic Chemistry
Article
Kehr, G.; Frohlich, R.; Grimme, S.; Erker, G. J. Am. Chem. Soc. 2009,
̈
131, 12280. (e) Stirling, A.; Hamza, A.; Rokob, T. A.; Papai, I. Chem.
Commun. 2008, 3148. (f) Guo, Y.; Li, S. H. Eur. J. Inorg. Chem. 2008,
2501.
(19) (a) Bebbington, M. W. P.; Bontemps, S.; Bouhadir, G.; Bourissou,
D. Angew. Chem., Int. Ed. 2007, 46, 3333. (b) Moebs-Sanchez, X.;
Bouhadir, G.; Saffon, N.; Maron, L.; Bourissou, D. Chem. Commun. 2008,
3435. (c) Momming, C. M.; Kehr, G.; Wibbeling, B.; Frohlich, R.; Erker,
̈
̈
G. Dalton Trans. 2010, 39, 7556. (d) Stute, A.; Kehr, G.; Frohlich, R.;
̈
Erker, G. Chem. Commun. 2011, 47, 4288.
(20) (a) Otten, E.; Neu, R. C.; Stephan, D. W. J. Am. Chem. Soc.
2009, 131, 9918. (b) Neu, R. C.; Otten, E.; Stephan, D. W. Angew.
Chem., Int. Ed. 2009, 48, 9709. (c) Neu, R. C.; Otten, E.; Lough, A.;
Stephan, D. W. Chem. Sci. 2011, 2, 170.
(21) Cardenas, A. J. P.; Culotta, B. J.; Warren, T. H.; Grimme, S.;
Stute, A.; Frohlich, R.; Kehr, G.; Erker, G. Angew. Chem., Int. Ed. 2011,
̈
DOI: 10.1002/anie.201101622.
(22) (a) Birkmann, B.; Voss, T.; Geier, S. J.; Ullrich, M.; Kehr, G.;
Erker, G.; Stephan, D. W. Organometallics 2010, 29, 5310. (b) Kreitner,
C.; Geier, S. J.; Stanlake, L. J. E.; Caputo, C.; Stephan, D. W. Dalton
Trans. 2011, 6771.
(23) (a) Welch, G. C.; Cabrera, L.; Chase, P. A.; Hollink, E.; Masuda,
J. D.; Wei, P. R.; Stephan, D. W. Dalton Trans. 2007, 3407. (b) Welch,
G. C.; Prieto, R.; Dureen, M. A.; Lough, A. J.; Labeodan, O. A.;
Holtrichter-Rossmann, T.; Stephan, D. W. Dalton Trans. 2009, 1559.
(24) Welch, G. C.; Juan, R. R. S.; Masuda, J. D.; Stephan, D. W.
Science 2006, 314, 1124.
(25) Arduengo, A. J.; Krafczyk, R.; Schmutzler, R.; Craig, H. A.;
Goerlich, J. R.; Marshall, W. J.; Unverzagt, M. Tetrahedron 1999, 55,
14523.
(26) Repeated attempts to obtain satisfactory C analysis were
consistently low in comparison to anticipated values. This was
attributed to the formation of metal-carbide during combustion.
(27) (a) Dorn, H.; Jaska, C. A.; Singh, R. A.; Lough, A. J.; Manners, I.
Chem. Commun. 2000, 1041. (b) Pringle, P. G.; Smith, M. B. J. Chem.
Soc., Chem. Commun. 1990, 1701. (c) Han, L.-B.; Tanaka, M. J. Am.
Chem. Soc. 1996, 118, 1571. (d) Wicht, D. K.; Kourkine, I. V.; Lew,
B. M.; Nthenge, J. M.; Glueck, D. S. J. Am. Chem. Soc. 1997, 119, 5039.
(e) Costa, E.; Pringle, P. G.; Worboys, K. Chem. Commun. 1998, 49.
(f) Han, L.-B.; Choi, N.; Tanaka, M. Organometallics 1996, 15, 3259.
(g) Powell, J.; Fuchs, E.; Gregg, M. R.; Phillips, J.; Stainer, V. R.
Organometallics 1990, 9, 387.
(28) (a) Siedle, A. R.; Newmark, R. A.; Gleason, W. B. Inorg. Chem.
1991, 30, 2005. (b) Albinati, A.; Lianza, F.; Pasquali, M.; Sommovigo,
M.; Leoni, P.; Pregosin, P. S.; Ruegger, H. Inorg. Chem. 1991, 30, 4690.
(c) Dingle, T. W.; Dixon, K. R. Inorg. Chem. 1974, 13, 846.
(29) (a) Bontemps, S.; Sircoglou, M.; Bouhadir, G.; Puschmann, H.;
Howard, J. A. K.; Dyer, P. W.; Miqueu, K.; Bourissou, D. Chem.Eur.
J. 2008, 14, 731. (b) Thomas, J. C.; Peters, J. C. J. Am. Chem. Soc.
2001, 123, 5100.
4721
dx.doi.org/10.1021/ic2026895 | Inorg. Chem. 2012, 51, 4711−4721