Metal-Coordinated White Phosphorus
FULL PAPER
obtained from a diluted CH2Cl2/n-hexane (1:1) solution by slow concen-
motion oscillating from the Ru-bonded P atom to the unme-
tration under nitrogen. The crystals were filtered off and dried in the air.
talated one, while the second pro
ACHTUNGTNERcNUNG ess, indicated as platinum
1H NMR (400 MHz, CD2Cl2, 295 K): d=7.91–6.86 (m, 40H; Ph), 4.88
motion, accounts for the {Pt(PPh3)2} ride along the three
AHCTUNGTRENNUNG
2
(br s, 2H; CH2), 4.56 (bs, 2H; CH2), ꢀ3.69 ppm (brd, 1H, JH,P
=
trans
162 Hz; Ru-H); 31P{1H} NMR (400 MHz, CD2Cl2, 295 K): d=ꢀ2.5 (d,
1JP =23 Hz; PA, 4P), ꢀ373.4 (q, 1JP =224 Hz; PM, 1P), ꢀ492.5 ppm
P atoms not coordinated to ruthenium.
Currently we are investigating the reactivity of these
monoACHTUNGTRENNUNGnuclear and dinuclear tetraphosphorus derivatives to-
wards different reagents and expanding the class of co-li-
gands at both ruthenium and platinum to provide a rationale
to the observed dynamic behavior.
APM
MPQ
(d, 1JP =224 Hz; PQ, 3P); IR (CH2Cl2): n˜(RuꢀH) =1975 cmꢀ1; MS (ESI):
MPQ
m/z: 995.07 (1+); elemental analysis calcd (%) for C50H45BF4P8Ru
(1081.56): C 55.53, H 4.19; found: C 55.71, H 4.25.
Synthesis of trans-[Ru
white phosphorus in THF (0.1m, 2.22 mL, 0.229 mmol) was syringed into
a solution of trans-[Ru(dppe)2(H)2] (200 mg, 0.229 mmol) and HBF4.EtO2
ACHTUNGTRENN(UNG dppe)2(H)AHCTUNGTRENNGNU A solution of
(h1-P4)]BF4 ([2]BF4):
AHCTUNGTRENNUNG
(31 mL, 1 equiv) in a mixture of THF (10 mL) and CH2Cl2 (6 mL). After
30 min the resulting brown solution was concentrated under vacuum. Ad-
dition of 20 mL of diethyl ether gave an ivory colored solid which was fil-
tered off and washed with toluene (25 mL). Yield: 89%, 222 mg. Crystals
suitable for X-ray analysis were obtained from a diluted CH2Cl2/n-
hexane (1:1) solution by slow concentration under nitrogen. The crystals
were filtered off and dried in the air. 1H NMR (400 MHz, CD2Cl2,
295 K): d=7.69–6.39 (m, 40H; Ph), 2.43 (m, 4H; C2H4), 2.11 (m, 4H;
Experimental Section
General details: All reactions and manipulations were carried out under
nitrogen using standard Schlenk glassware and techniques. Dichloro
ACHTUNGTRENNUNGane was purified by distillation over CaH2. THF was purified by distilla-
tion over sodium wire and benzophenone. Diethyl ether and n-pentane
were purified by passing them over two columns filled with molecular
sieves (4 ꢃ) (LabMaster MBRAUN MD SPS). n-Hexane was used as
purchased. Deuterated solvents (Aldrich) were pre-treated with three
freeze-thaw pump cycles before use and kept under an inert atmosphere.
ACHTUNGTNERmNUNG eth-
2
C2H4), ꢀ5.68 ppm (brd, 1H; Ru-H, JH,P =175 Hz); 31P{1H} NMR
trans
(400 MHz, CD2Cl2, 295 K): d=60.6 (d, 1JP =20 Hz; 4P, PA), ꢀ380.4 (q,
APM
1JP =221 Hz; PM, 1P), ꢀ492.5 ppm (d, 1JP =221 Hz; PQ, 3P); IR
MPQ
MPQ
(CH2Cl2): n˜(RuꢀH) =1975 cmꢀ1; MS (ESI): m/z: 933.36 (2+); elemental
analysis calcd (%) for C52H49BF4P8Ru (1109.24): C 56.25, H 4.45; found:
C 56.41, H 4.72.
Literature methods were used for the preparation of [Pt
(PPh3)2],[26] [Ru(dppm)2(H)2],[27] [Ru (h2-H2)]BF4,[28] [Ru-
(dppm)2(H)
(dppe)2(H)2],[29] [CpRu (h1-P4)]PF6,[17] [CpOs (h1-P4)]PF6,[30]
(PPh3)2A (PPh3)2A
and [(triphos)Re(CO)2A (dppe)
(h1-P4)]OTf.[6] The syntheses of [Cp*Ru (h1-
P4)]PF6 and [Cp*Fe(dppe)
(h1-P4)]PF6 were carried out according to the
ACHTUGNTERN(NUGN C2H4)-
G
E
A
ACHTUNGTRENNUNG
R
A
U
E
CHTUNGTRENNUNG
Improved synthesis of [Cp*Ru
(PPh3)2Cl]:[31]
A
suspension of
C
G
ACHTUNGTRENNUNG
[Cp*RuCl2]2 (0.5 g, 1.64 mmol), PPh3 (1.73 g, 6.6 mmol) and an excess of
zinc dust in THF (65 mL) was stirred for 2 h. The solution was filtered
and transferred to another flask containing n-pentane (200 mL). Upon
15 min formation of orange crystals was observed. After precipitation
was complete (1 h), the crystals were filtered off and dried under nitro-
gen. Yield: 90%, 0.58 g.
[12]
U
ACHTUNGTRENNUNG
literature with only slight modifications as explained below.
Solution multinuclear NMR spectra were recorded on
a
Bruker
Avance 400 spectrometer, equipped with a variable temperature control
unit. 31P{1H} EXSY spectra were recorded by using the library pulse pro-
gram “noesyph” modified for 1H decoupling. Line-shape analysis was
performed by DNMR module of TopSpin BRUKER. DG° values were
calculated at 298 K. 1H chemical shifts are referenced to tetramethylsi-
lane (TMS), 31P chemical shifts are referenced to 85% H3PO4
(161.92 MHz), and 195Pt chemical shifts are referenced to H2PtCl6
(85.98 MHz). Solid-state NMR spectra at 9.4 T (n0 =161.9 MHz) were re-
corded at ambient temperature (296 K) on a BRUKER AVANCE 400
spectrometer equipped with a 4 mm MAS probe. All spectra were ac-
quired using magic angle spinning (MAS) at spinning speeds between 9
and 14 kHz, and high power 1H decoupling was applied during acquisi-
tion. All experiments were recorded with pulse sequences from the
standard BRUKER pulse program library. Two-dimensional EXSY spec-
tra were recorded using rotor synchronized mixing times[24] and
908 pulses of 3.9 ms duration. Cross polarization with a ramp-shaped con-
tact pulse and mixing times of 5 ms was used for signal enhancement in
measurements of CP MAS spectra of [3]PF6. The presence of solvent in
Synthesis of [Cp*Ru
white phosphorus (0.1m, 1.94 mL, 0.194 mmol) was added to a solution
of [Cp*Ru(PPh3)2Cl] (200 mg, 0.194 mmol) and TlPF6 (101 mg,
(h1-P4)]PF6 ([5]PF6): A THF solution of
ACHUTNGTREN(NUG PPh3)2ACHTUTGNRENNUGN
AHCTUNGTRENNUNG
0.289 mmol) in a mixture of CH2Cl2 (5 mL) and THF (4 mL). The result-
ing slurry was stirred at ꢀ508C for 2 h; the TlCl which separated out was
(h1-P4)]PF6 was obtained as orange micro-
filtered off and [CpRuACHTNUGTRENNUG(PPh3)2ACHTUTGNRENNUGN
crystals by evaporating the solvent under reduced pressure. Yield: 90%,
231 mg. Crystals suitable for X-ray analysis were obtained by layering
Et2O (50 mL) over the CH2Cl2/THF solution. 1H NMR (400 MHz,
CD2Cl2, 295 K): d=7.50–6.94 (m, 30H; Ph), 1.30–1.25 ppm (m, 15H; C5-
A
=
APM
57 Hz; 4P, PA), ꢀ330.8 (qt, 1JP =227 Hz, 2JP =57 Hz; 1P, PM),
ꢀ492.5 ppm (d, 1JP =227 Hz; 3P, PQ), MS (ESI): m/z: 885.1 (5+); ele-
mental analysis calcd (%) for C46H45P7RuF6 (1029.72): C 53.65, H 4.40;
found: C 53.76, H 4.63.
(h1-P4)]PF6 ([6]PF6):[12] A THF sol-
ACHUTGTNRNEUG(N dppe)ACHTUTGNRENNUGN
1
Improved synthesis of [Cp*Ru
ution of white phosphorus (0.1m, 2.49 mL, 0.249 mmol) was added to a
solution of [Cp*Ru(dppe)Cl] (200 mg, 0.249 mmol) and TlPF6 (87 mg,
the used sample of [3]PF6 was verified by solution H NMR spectroscopy.
IR spectra were recorded with a Spectrum BX II Perkin–Elmer spec-
trometer; ESI-MS analyses were performed using a Finnigan Analytic
LTQ instrument. High resolution mass spectrometry (HRMS) analyses
were performed using a time-of-flight mass spectrometer equipped with
an electro-spray ion source (Bruker micrOTOF-Q II). The analyses were
carried out in positive ion mode. The sample solutions were introduced
by continuous infusion with the aid of a syringe pump at a flow-rate of
180 mLhꢀ1. The instrument was operated at end plate offset ꢀ500 V and
capillary 4500 V. Nebulizer pressure was 0.3 bar (N2) and the drying gas
(N2) flow 4 Lminꢀ1. Drying gas temperature was set at 1808C. The soft-
ware used for the simulation is Bruker Daltonics DataAnalysis (ver-
sion 4.0).
AHCTUNGTRENNUNG
0.249 mmol) in a mixture of CH2Cl2 (5 mL) and THF (4 mL). The result-
ing slurry was stirred at room temperature for 2 h; the precipitated TlCl
(h1-P4)]PF6 was obtained as orange crys-
was filtered off and [CpRuACTHNUTRGENNGU(dppe)AHCTUNGTRENNGUN
tals by layering Et2O (50 mL) over the CH2Cl2/THF solution. Yield:
90%, 243 mg.
Improved synthesis of [Cp*Fe
tion of white phosphorus (0.1m, 3.19 mL, 0.319 mmol) was added to a sol-
ution of [Cp*Fe(dppe)Cl] (200 mg, 0.319 mmol) and NH4PF6 (80 mg,
(h1-P4)]PF6 ([7]PF6):[12] A THF solu-
ACHUTGTNRNEUG(N dppe)ACHTUTGNRENNUGN
AHCTUNGTRENNUNG
0.480 mmol) in a mixture of CH2Cl2 (12 mL) and THF (8 mL). The re-
sulting slurry was stirred at room temperature overnight; the precipitated
(h1-P4)]PF6 was obtained as
NH4Cl was filtered off and [Cp*FeACTHUNTGRENNUG(dppe)CAHTUNGTRENNUGN
Synthesis of trans-[Ru
white phosphorus in THF (0.1m, 2.29 mL, 0.229 mmol) was syringed into
a solution of trans-[Ru(dppm)2(H)
(h2-H2)]BF4 (200 mg, 0.229 mmol) in
(h1-P4)]BF4 ([1]BF4): A solution of
ACHTUNGTRENNUNG(dppm)2(H)ACHTUGNTRENNUGN
purple microcrystals by evaporating the solvent under reduced pressure.
Yield: 80%, 219 mg.
A
ACHTUNGTRENNUNG
CH2Cl2 (10 mL). After 15 min the resulting dark brown solution was con-
centrated under vacuum. Addition of 20 mL of diethyl ether gave an
ivory colored solid which was filtered off and washed with toluene
(25 mL). Yield: 84%, 209 mg. Crystals suitable for X-ray analysis were
Synthesis of trans-[{Ru
N
A
ACHTUNGTRENNUNG([1-
Pt]BF4): Solid [Pt(C2H4)(PPh3)2] (140 mg, 0.183 mmol) was added por-
A
ACHTUNGTRENNUNG
tion-wise to a solution of [1]BF4 (200 mg, 0.183 mmol) in 10 mL of
CH2Cl2 under nitrogen at room temperature. After stirring for 5 min, the
Chem. Eur. J. 2012, 00, 0 – 0
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!
Mirabello, Vincenzo
