Group 8 transition metal complexes of the tripodal triphosphino ligands PhSi(CH2PR2)3 (R = Ph, iPr)

Article abstract of DOI:10.1002/ejic.201301074

A series of group 8 transition metal complexes of new tridentate phosphine ligands with Fe, Ru, and Os were prepared. The new complexes were characterized by multinuclear NMR spectroscopy and X-ray crystallography. Complexes of iron, ruthenium, and osmium with the neutral tridentate tripodal phosphine ligands PhSi(CH₂PPh₂)₃ and PhSi(CH₂PiPr ₂)₃ show tetrahedral coordination for iron and form cationic dimeric octahedral complexes with the heavier homologues ruthenium and osmium. Copyright

Full text of DOI:10.1002/ejic.201301074

SHORT COMMUNICATION
DOI:10.1002/ejic.201301074
Group 8 Transition Metal Complexes of the Tripodal
Triphosphino Ligands PhSi(CH2PR2)3 (R = Ph, iPr)
Felix Neumeyer,[a,b] Michael I. Lipschutz,[a] and T. Don Tilley*[a]
Keywords: Tridentate ligands / Iron / Ruthenium / Osmium / Phosphane
A series of group 8 transition metal complexes of new triden-
tate phosphine ligands with Fe, Ru, and Os were prepared.
The new complexes were characterized by multinuclear
NMR spectroscopy and X-ray crystallography.
three equivalents of trichlorophenylsilane to give neutral
tridentate ligands 1a and 1b (Scheme 1).
Introduction
Tripodal ligands have played important roles in coordi-
nation chemistry and catalysis.[1] Generally, such ligands are
used to enforce specific coordination geometries or to func-
tion as crucial ancillary ligands in metal-mediated chemis-
try. For four-coordinate complexes, such ligands may oc-
cupy three coordination sites, thereby leaving one reactive
site free to engage in chemical transformations. For octahe-
dral complexes, tripodal ligands may bind in facial manner
to provide rigorously defined coordination geometries. Tri-
podal triphosphine ligands designed to bind in this way in-
Scheme 1. Synthesis of 1a and 1b, and reactions with iron di-
chloride to give 2a and 2b.
Complex 1a is a colorless solid, whereas 1b is a viscous
clude [PhB(CH2PPh2)3]–,[2] MeC(CH2PPh2)3 (triphos),[3] colorless oil. Phenyl-substituted compound 1a exhibits a
tBuSi(CH2PMe2)3,[4] and MeSi(CH2PMe2)3.[5] These latter 31P{1H} NMR shift (–23.59 ppm) that is significantly up-
neutral tridentate tripodal phosphine ligands were pre- field of that for the corresponding isopropyl derivative 1b
viously employed to stabilize highly reactive iron(0) com- (–5.14 ppm).
plexes for vicinal dichlorine elimination at dichloroalk-
Reaction of 1a with iron dichloride suspended in THF
enes[6,7] or heterodinuclear trihydride complexes of rhodium gave iron(II) complex 2a as a colorless solid in good yield
and iron for hydrogenations and C–H activation reac- (Scheme 1). NMR spectroscopic data were not obtainable
tions.[8] For ruthenium, they have also been used in mechan- because of the paramagnetic nature of the compound. By
istic studies of C–C and C–H bond activations.[9–11] In this Evans’ method,[14] 2a is a high-spin iron(II) complex (S = 2,
contribution we report new triphosphines PhSi(CH2PPh2)3 μeff = 4.83 μB). Complex 2a possesses a tetrahedral iron(II)
(1a) and PhSi(CH2PiPr2)3 (1b). For comparative purposes center as determined by X-ray crystallography (see Sup-
these were used as ligands to prepare complexes of the porting Information).
group 8 metals iron, ruthenium, and osmium.
Only two phosphorus atoms are bound to the metal cen-
ter, resulting in Fe–P distances of 2.480(1) and 2.449(1) Å,
and one phosphorus atom remains unbound to the metal
center. Interestingly, the less sterically demanding triphos-
phine MeSi(CH2PMe2)3 forms the diiron ionic compound
{[MeSi(CH2PMe2)3]2Fe2(μ-Cl)3}Cl with octahedral metal
centers.[15] The Fe–Cl bond lengths in 2a are 2.207(1) and
2.245(1) Å. Also, the pseudo-tetrahedral geometry in 2a re-
sults in a relatively large Cl–Fe–Cl bond angle of 117.30(4)°,
which is similar to the value reported in a related four-coor-
dinate iron(II) dichloride complex.[16] The chelation of the
phosphine ligand results in a small P–Fe–P bond angle of
94.05(4)°.
Results and Discussion
Following established procedures, diphenylmethyl-
phosphine (Ph2PCH3) and diisopropylmethylphosphine
(iPr2PCH3) were deprotonated[12,13] and then treated with
[a] Department of Chemistry, University of California, Berkeley,
Berkeley, California 94720-1460, USA
E-mail: tdtilley@berkeley.edu
http://www.cchem.berkeley.edu/tdtgroup/
[b] Current address: Institut für Anorganische Chemie,
Johann Wolfgang Goethe-Universität Frankfurt am Main,
Max-von-Laue-Str. 7, 60438 Frankfurt am Main, Germany,
http://www.anorg.chemie.uni-frankfurt.de
Reaction of 1b and iron dichloride gave the related com-
plex 2b. The structural and metrical parameters of 2b are
similar to those of 2a (Figure 1). The Fe–P as well as the
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301074.
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Fe–Cl bond lengths are nearly identical in comparison to 2.31(1) Å, respectively. Ruthenium is in a slightly distorted
2a (within 0.02 Å). A notable difference corresponds to octahedron with trans P–Ru–Cl bond angles of about
larger Cl–Fe–Cl [122.72(2)°] and P–Fe–P [97.86(2)°] angles 170(2)°, and the cis P–Ru–Cl bond angles average 95(2)°.
for 2b, apparently the result of more sterically demanding
phosphino groups in the latter complex.
Scheme 2. Synthesis of ruthenium and osmium complexes by using
1a and 1b.
Following a similar synthetic procedure, dimeric osmium
bromide complexes 4a and 4b containing ligands 1a and 1b
were prepared. The 31P{1H} NMR spectra for 4a and 4b
exhibit a single resonance, at –30.00 and –21.67 ppm,
respectively. The crystal structure of 4a (Figure 2) reveals a
dimer with slightly distorted octahedra for both osmium
Figure 1. ORTEP diagram of 2b (left) and 5 (right) with thermal
centers, as found for the ruthenium analogue 3a. For this
structure, the mean Os–Br bond length is 2.61(2) Å, the
mean Os–P bond length is 2.314(8) Å, and the Os–Os sepa-
ration is 3.603(1) Å. The crystal structure of 4b (see Sup-
porting Information) reveals slight elongations of the mean
Os–Br [by 0.02(1) Å], Os–P [by 0.011(7) Å], and Os–Os [by
0.085(1) Å] distances, with respect to comparable param-
eters in 4a. This can be attributed to the higher steric de-
mand of the isopropyl groups, which enforce a greater sepa-
ration between the osmium centers.
ellipsoids shown at the 50% probability level. Hydrogen atoms are
omitted for clarity. Selected bond lengths [Å] and angles [°]: 2b: Fe–
Cl1 2.2239(6), Fe–Cl2 2.2589(5), Fe–P1 2.4233(6), Fe–P2 2.4403(5);
Cl1–Fe–Cl2 122.72(2), P1–Fe–P2 97.86(2). 5: Fe–Cl 2.271(1), Fe–
P1 2.297(1), Fe–P2 2.305(1), Fe–P2 2.304(1); P1–Fe–P2 101.54(4),
P1–Fe–P3 102.76(4), P2–Fe–P3 101.63(4), P1–Fe–Cl 114.85(5), P2–
Fe–Cl 115.89(5), P3–Fe–Cl 117.85(5).
Complex 2b was reduced by KC8 to green iron(I) com-
plex PhSi(CH2PiPr2)3FeCl (5). While the Fe–Cl bond length
[2.271(1) Å] remains unchanged in comparison to that in
compound 2b, the Fe–P bond lengths are shortened by
slightly more than 0.1 Å [to an average value of 2.302(4) Å,
Figure 1]. This Fe–P bond length is approximately 0.1 Å
shorter than those found in iron(II) complexes featuring the
tripodal [PhB(CH2PPh2)3]–[17] and [PhB(CH2PiPr2)3]– li-
gands.[18] The Fe–P bonds in 5 are also similar in length
(within 0.02 Å) to Fe–P bonds in iron(I) compounds with
the [PhB(CH2PPh2)3]– ligand.[17] The P–FeI–P bond angles
in 5 [102.0(7)°] are significantly greater than those in
iron(II) complexes of [PhB(CH2PPh2)3]– [92(2)°][17] or
[PhB(CH2PiPr2)3]– [93.9(6)°].[18] These differences may be
caused by the larger size of silicon relative to boron, which
allows ligand 1b to accommodate a larger bite angle for
the phosphorus atoms bound to iron, thus forming a more
tetrahedral complex.
Ruthenium analogues 3a and 3b were prepared by re-
fluxing a toluene suspension of dichloro(1,5-cycloocta-
dienyl)ruthenium(II) ([COD]RuCl2) with 1a or 1b
(Scheme 2). Both complexes were isolated as orange solids.
These complexes exhibit a single resonance in the 31P{1H}
NMR spectrum, at 29.44 (3a) and 39.19 ppm (3b). A single
crystal of 3a was obtained by layering diethyl ether on a
concentrated solution of 3a in dichloromethane. As deter-
mined by single-crystal X-ray diffraction analysis, 3a pos-
sesses a dimeric structure in which each ruthenium core has
Figure 2. ORTEP diagram of 4a with thermal ellipsoids shown at
the 50% probability level. Hydrogen atoms are omitted for clarity.
Selected bond lengths [Å] and angles [°]: Os1–Br1 2.6320(6), Os1–
Br2 2.5844(8), Os1–Br3 2.6231(7), Os1–P1 2.326(2), Os1–P2
2.303(2), Os1–P3 2.318(2); P2–Os1–Br2 167.82(5), P3–Os1–Br1
168.80(5), P2–Os1–P3 92.28(6).
The Os–Os distances in 4a and 4b [3.603(1) and
an octahedral environment. Three chlorine atoms are bridg- 3.688(1) Å] are longer in comparison with those in related
ing between the ruthenium centers, while one remaining diosmium complexes presumed to lack metal–metal bond-
chloride is outer-sphere (see Supporting Information). The ing, such as [H4(PiPr3)4Os2(μ-Cl)3]CF3SO4 [3.539(1) Å],[19]
average Ru–Cl and Ru–P bond lengths are 2.478(9) and [(PEt3)6Os2(μ-Cl)3]PF6 [3.474(1) Å],[20] and [(PEt2Ph)6Os2-
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(μ-Cl)3]Cl [3.465(1) Å].[21] These differences might corre-
spond to the larger bromine atoms bridging between the
osmium centers.
ually warmed to room temperature with stirring, over the course
of 14 h. Removal of the solvent under reduced pressure gave a
brown oil. The oil was extracted into pentane (100 mL), passed
through a short column of silica gel (5 cmϫ2 cm), and then
washed with additional pentane (100 mL) and diethyl ether
(100 mL). The solvents were again removed under reduced pres-
sure. A colorless oil was obtained (1.51 g, 3.03 mmol, 68%). 1H
NMR (C6D6): δ = 8.01–7.98 (m, 2 H, ArH), 7.27–7.18 (m, 3 H,
ArH), 1.64 (sept., J = 7.1, 1.1 Hz, 6 H, CH), 1.20 (d, J = 2.8 Hz,
6 H, CH2), 1.09–1.01 (m, 36 H, CH3) ppm. 13C{1H} NMR (C6D6):
δ = 139.42–139.38 (m), 135.45 (q, JPC = 2.4 Hz), 129.53, 128.35,
127.73, 25.29 (d, JPC = 16.7 Hz), 19.97 (d, JPC = 13.8 Hz), 19.73
(d, JPC = 13.7 Hz), 6.46 (dt, JPC = 38.5, 5.4 Hz) ppm. 31P{1H}
Conclusions
A series of group 8 transition metal complexes with two
new tripodal triphosphine ligands were prepared and char-
acterized. Iron(II) complexes of these ligands possess
pseudo-tetrahedral geometries for the iron centers and a
“dangling” phosphino group. However, an FeI analogue ex-
hibits bonding to all three phosphorus donors in an ap-
proximate tetrahedral coordination geometry. For the larger
ruthenium and osmium atoms, octahedral complexes were
obtained. In these cases a cationic, dimeric structure with
NMR (C6D6):
δ = δ = –5.1 ppm.
–5.14 ppm. 29Si NMR:
C27H53P3Si (498.7): calcd. C 65.02, H 10.71; found C 64.80, H
10.49.
PhSi(CH2PPh2)3FeCl2 (2a):
A suspension of iron dichloride
three halogen atoms bridging between each metal center is (13.8 mg, 0.11 mmol) in THF (5 mL) was stirred for 30 min. A
solution of 1a (75.0 mg, 1.06 mmol) in THF (1 mL) was then slowly
added to the light orange-brown suspension of FeCl2. The resulting
mixture was stirred for 24 h, and then the solvent was removed
under reduced pressure. The remaining residue was extracted into
toluene (10 mL) and filtered through a plug of Celite. The solvent
was again removed under reduced pressure. A colorless solid was
obtained, which was then washed with pentane (2ϫ5 mL). The
isolated product was dried under vacuum to give colorless 2a
(76 mg, 0.09 mmol, 84%). μeff (C6D6) = 4.83 μB. EI MS: m/z = 828
[M]+. C45H41Cl2FeP3Si (829.6): calcd. C 65.15, H 4.98; found C
65.54, H 5.04.
observed. Compounds 4a and 4b are to the best of our
knowledge the first osmium complexes that feature a tri-
podal triphosphine ligand. Studies of the coordination and
organometallic chemistry of the complexes mentioned
above is the goal of future work.
Experimental Section
General: Manipulations involving air-sensitive compounds were
conducted by using standard Schlenk techniques in a purified ni-
trogen atmosphere or in a nitrogen glove box. Solvents were dried
with a VAC drying system and stored in PTFE-valved flasks. Deu-
terated solvents (Cambridge Isotopes) were dried with appropriate
drying agents and vacuum-transferred before use. NMR spectra
were acquired with Bruker AVB-400, AVQ-400, AV-500, or AV-600
spectrometers. Spectra were recorded at room temperature and
were referenced to protic impurities.[22] 31P{1H} NMR spectra were
referenced to an 85% H3PO4 external standard (δ = 0 ppm).
PhSi(CH2PiPr2)3FeCl2 (2b): The same procedure used for the syn-
thesis of 2a was employed, starting from 1b. Yield: 1.60 g,
2.56 mmol, 85%. μeff (C6D6) = 4.90 μB. EI MS: m/z = 624 [M]+.
C27H53Cl2FeP3Si (625.5): calcd. C 51.85, H 8.54; found C 51.70, H
8.53.
{[PhSi(CH2PPh2)3]2Ru2(μ-Cl)3}Cl (3a): [(COD)RuCl2]n (67 mg,
0.24 mmol) was placed in a Teflon-sealed NMR tube, and to this
solid was added 1a (174 mg, 0.25 mmol) in toluene (1 mL). The
resulting suspension was heated to 125 °C for 21 h. The red-orange
suspension was extracted into dichloromethane (2ϫ2 mL) and
then filtered through a plug of Celite. After evaporation of the sol-
vent, the resulting orange powder was washed with diethyl ether
(2 mL) and then dried under vacuum to give 3a (178 mg,
0.10 mmol, 82%). Crystals suitable for X-ray diffraction were ob-
tained by layering a concentrated solution of 3a in dichlorometh-
Tris[diphenylphosphinomethyl]phenylsilane
(1a):
Ph2PCH2Li·
TMEDA[12] (4.47 g, 13.9 mmol) was dissolved in toluene (150 mL),
and the resulting solution was cooled to –78 °C. Trichlorophenylsi-
lane (0.92 g, 4.33 mmol) dissolved in toluene (1 mL) was slowly
added to the reaction mixture with a syringe. The solution was
gradually warmed to room temperature over the course of 20 h.
Removing the solvent under reduced pressure gave a cloudy yellow
oil. The oil was extracted with pentane (100 mL) and diethyl ether
(200 mL). The combined extracts were then filtered through a plug
of silica. The solvent was then evaporated under reduced pressure,
and the resulting yellow oil was washed with hot methanol (50 mL).
The solvent was decanted, and the remaining residue solidified
upon drying under vacuum (2.51 g, 3.57 mmol, 82%). 1H NMR
(C6D6): δ = 7.59 (dd, J = 7.4, 1.6 Hz, 2 H, ArH), 7.43–7.32 (m, 13
H, ArH), 7.12–6.95 (m, 24 H, ArH), 1.57 (s, 6 H, CH2) ppm.
13C{1H} NMR (C6D6): δ = 141.62 (d, JPC = 15.9 Hz), 136.13,
135.26, 133.15 (d, JPC = 20.9 Hz), 132.63, 132.45, 129.40, 128.51,
13.23–12.90 (m) ppm. 31P{1H} NMR (C6D6): δ = –23.59 ppm.
HRMS (ESI): calcd. for C45H42P3Si [M + H]+ 703.2263, found
703.2259.
1
ane with diethyl ether. H NMR (CD2Cl2): δ = 7.65–7.62 (m, 4 H,
ArH), 7.56–7.47 (m, 6 H, ArH), 7.36–7.23 (m, 36 H, ArH), 6.92 (t,
J = 7.5 Hz, 24 H, ArH), 1.95–1.93 (m, 12 H, CH2) ppm. 13C{1H}
NMR (CD2Cl2): δ = 138.67–138.23 (m), 134.3, 133.92, 131.7,
130.03, 129.34, 128.03, 11.39–11.28 (m) ppm. 31P{1H} NMR
(CD2Cl2): δ = 29.44 ppm. C90H82Cl4P6Ru2Si2·CH2Cl2 (1749.6 +
84.9): calcd. C 59.58, H 4.62; found C 59.28, H 4.75.
{[PhSi(CH2PiPr2)3]2Ru2(μ-Cl)3}Cl (3b): The same procedure used
for the synthesis of 3a was employed, starting from 1b. Yield:
1
120 mg, 0.09 mmol, 82%. H NMR (CD2Cl2): δ = 7.57–7.53 (m, 4
H, ArH), 7.49–7.43 (m, 6 H, ArH), 2.58–2.38 (m, 12 H, CH2),
1.64–1.49 (m, 32 H, iPrH), 1.38–1.26 (m, 40 H, iPrH), 1.19–1.13
(m, 12 H, iPrH) ppm. 13C{1H} NMR (CD2Cl2): δ = 134.14, 129.11,
33.2, 22.23, 21.61, 21.41, 4.34 ppm. 31P{1H} NMR (CD2Cl2): δ =
39.19 ppm. C54H106Cl4P6Ru2Si2 (1341.4): calcd. C 48.35, H 7.97;
found C 47.97, H 7.97.
Tris[diisopropylphosphinomethyl]phenylsilane (1b): iPr2PCH2Li[13]
(1.95 g, 14.12 mmol) was dissolved in THF (30 mL), and the re-
sulting solution was cooled to –78 °C. Trichlorophenylsilane
(0.94 g, 4.44 mmol) dissolved in THF (2 mL) was slowly added to
the reaction mixture with a syringe. The reaction mixture was grad-
{[PhSi(CH2PPh2)3]2Os2(μ-Br)3}Br (4a): The same procedure used
for the synthesis of 3a was employed, starting from 1a and [(COD)-
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OsBr2]n, and this resulted in a yellow-green solid. Yield: 810 mg,
Acknowledgments
0.39 mmol, 56%. 1H NMR (CD2Cl2): δ = 7.66 (d, J = 7.0 Hz, 4 H,
ArH), 7.57–7.51 (m, 6 H, ArH), 7.34–7.24 (m, 36 H, ArH), 7.11 (t,
J = 7.4 Hz, 24 H, ArH), 2.2 (d, J = 8.0 Hz, 12 H, CH2) ppm.
13C{1H} NMR (CD2Cl2): δ = 138.51–138.18 (m), 134.43, 133.43,
131.71, 130.08, 129.41, 128.07, 10.11–9.97 (m) ppm. 31P{1H} NMR
(CD2Cl2): δ = –30.00 ppm. C90H82Br4Os2P6Si2 (2105.7): calcd. C
51.34, H 3.93; found C 50.80, H 4.23.
This work was funded by the National Science Foundation under
Grant No. CHE-1265674. The authors thank Mark C. Lipke and
Dr. Meg E. Fasulo for assistance with X-ray crystallography.
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31P{1H} NMR (CD2Cl2): δ = –21.67 ppm. C54H106Br4Os2P6Si2
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(49 mg, 0.37 mmol) in toluene (1 mL). The mixture was allowed to
stand for 30 min at –35 °C before being allowed to gradually warm
to room temperature. It was then stirred for 16 h. The dark reaction
mixture was then filtered through Celite to give a dark red solution.
The solution was concentrated to approx. 0.5 mL and then pentane
(3 mL) was added, whereupon green solids precipitated. The mix-
ture was stored for 16 h in the freezer. The red solution was de-
canted from the green solids, which were washed with cold pentane
(2ϫ 1 mL) and then dried under vacuum (80 mg, 0.14 mmol, 55%).
UV/Vis (THF): λmax (ε, m–1 cm–1) = 741 (607), 312 (5157), 265
(6071), 210 (26458) nm. μeff (C6D6) = 4.50 μB. C45H41ClFeP3Si
(794.1): calcd. C 54.96, H 9.05; found C 54.46, H 8.71.
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CCDC-951146 (for 2a), -951142 (for 2b), -951144 (for 3a), -951143
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obtained free of charge from The Cambridge Crystallographic
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Supporting Information (see footnote on the first page of this arti-
cle): ORTEP diagrams of 2a, 3a and 4b, and further details of the
X-ray crystallographic structure determination.
Received: August 20, 2013
Published Online: November 19, 2013
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim