Alkyne-coordinating tridentate ligands: Structural properties and reactivity of their rhodium complexes

Article abstract of DOI:10.1039/c2dt31322g

Complexes of novel alkyne-chelating tridentate ligands bound to a rhodium atom were isolated and characterised. The present alkyne-rhodium complex underwent dimerisation simply by heating to afford the unprecedented cyclobutadiene dirhodium complex. It is also found that the ligands at the trans positions influence the π-coordination of alkynes.

Full text of DOI:10.1039/c2dt31322g

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
Alkyne-Coordinating Tridentate Ligands: Structural Properties and Reactivity of Their
Rhodium Complexes
Kazuhiro Okamoto,* Yusuke Omoto, Hayato Sano, and Kouichi Ohe*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto
University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
e-mail: kokamoto@scl.kyoto-u.ac.jp; ohe@scl.kyoto-u.ac.jp
Supporting Information
I. General. NMR spectra were recorded on a JEOL EX-400 spectrometer at 25 °C (400 MHz
for 1H NMR, 100 MHz for 13C NMR, and 162 MHz for 31P NMR). Chemical shifts are reported in
1
13
δ ppm referenced to CDCl3 (δ 7.26 for H NMR and δ 77.00 for C NMR). IR spectra were
recorded with an FT-IR spectrometer (JASCO FT/IR-460 Plus). Melting points (mp) are
uncorrected. MALDI-TOF mass spectra were obtained with 1,8-Dihydroxy-9(10H)-anthracenone
(DIT) as a matrix on a SHIMADZU KRATOS TOF MASS spectrometer AXIMA-CFR Plus.
High-resolution mass spectra (HRMS) were recorded on a JEOL JMX-SX 102A spectrometer.
Elemental analyses were not successful because of instability of a series of the rhodium complexes.
CH2Cl2 and THF were purified by passed through a neutral alumina column under argon
atmosphere. Hexane and benzene were distilled over sodium and benzophenone under nitrogen.
1
2
[RhCl(cod)]2
and NaBArF (sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate)
were
prepared according to the literatures. All other materials were purchased and used without further
purification.
II. Preparation of a ligand.
Bis(2-(diphenylphosphino)phenyl)acetylene (1) [CAS 345342-51-0]3
Ph2
P
Ph2
P
1
A typical procedure for the synthesis of ligands is shown below. To a stirred suspension of
t-BuOK (6.06 g, 54.0 mmol) in hexane (66 mL) and THF (92 mL) was added n-BuLi (1.6 N in
hexane solution, 28 mL, 44.0 mmol) dropwise at –78 °C over 15 min. After stirring for additional
15 min, diphenylacetylene (3.56 g, 20.0 mmol) dissolved in THF (20 mL) was added dropwise over
10 min. The mixture was stirred at –78 °C for 40 min, and then at –25 °C for 1.5 h. The
1 J. Chatt, J. Chem. Soc. 1957, 4753.
2 N. A. Yakelis and R. G. Bergman, Organometallics 2005, 24, 3579.
3 J. Kowalik and L. M. Tolbert, J. Org. Chem. 2001, 66, 3229.
S1

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
resulting solution was cooled to –43 °C, and chlorodiphenylphosphine (8.26 mL, 46.0 mmol) was
added dropwise over 10 min. The reaction mixture was warmed to room temperature over 5 h,
and quenched with degassed water (10 mL). The organic layer was separated, dried over MgSO4,
filtered, and concentrated under vacuum. The residue was recrystallized from hexane/CH2Cl2 to
give 3.64 g of ligand 1 (6.66 mmol, 33% yield) as a white powder. Mp 142.2 °C (dec). 1H NMR
(CD2Cl2): δ 6.79–6.81 (m, 2H), 7.12–7.15 (m, 2H), 7.16–7.24 (m, 4H), 7.32–7.37 (m, 20H). 13C
NMR (CD2Cl2): δ 95.3–95.4 (m), 127.9 (d, J = 30.1 Hz), 128.6 (d, J = 16.5 Hz), 128.899, 128.903
(d, J = 7.4 Hz), 129.2, 132.7, 132.8 (m), 134.4 (d, J = 20.7 Hz), 136.9 (d, J = 12.0 Hz), 140.7 (d, J
= 13.1 Hz). 31P NMR (CD2Cl2): δ –8.6. HRMS (FAB) calcd for C38H28P2 [M]+ 547.1745, found
547.1750.
III. Complexation with rhodium(I).
2
Cl
Ph2P
Rh
PPh2
2
A solution of ligand 1 (109.3 mg, 0.20 mmol) and [RhCl(cod)]2 (49.3 mg, 0.10 mmol) in dry
CH2Cl2 (15 mL) was stirred at room temperature for 15 min, and then dry hexane (30 mL) was
added to the reaction mixture. After the additional stirring for 1 h, the solvent was concentrated
by nitrogen flow. The precipitate was filtered, washed with hexane, and dried under vacuum to
give complex 2 as a red prism (119 mg, 0.17 mmol, 85%). Mp 85.0 °C (dec). 1H NMR
(CD2Cl2): δ 7.33–7.43 (m, 14H), 7.56 (t, J = 7.4 Hz, 2H), 7.60-7.64 (m, 2H), 7.74-7.80 (m, 8H),
8.05 (d, J = 7.6 Hz, 2H). 13C NMR (CD2Cl2): δ 101.7 (d, JC-Rh = 9.1 Hz), 128.1, 128.6 (virtual t,
JC–P sum = 10.0 Hz), 130.5, 131.4 (virtual t, JC–P sum = 18.0 Hz), 131.8, 133.7, 134.0 (virtual t, JC–P sum
=
6.8 Hz), 134.2 (virtual t, JC–P sum = 6.2 Hz), 138.2 (virtual t, JC–P sum = 37.8 Hz), 149.0 (virtual t, JC–P
= 51.6 Hz). 31P NMR (CD2Cl2): δ 46.5 (d, JRh-P = 122 Hz). HRMS (FAB) calcd for
sum
C38H28ClP2Rh [M]+ 684.0410, found 684.0415.
3
Ph2
P
Cl
PPh2
Rh
Rh
Ph2P
P
Ph2
Cl
3
S2

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
A solution of ligand 1 (10.9 mg, 20.0 μmol) and [RhCl(cod)]2 (4.9 mg, 10.0 μmol) in dry
benzene (1.5 mL) was stirred at 50 °C for 48 h (in the dark). The dark red crystal was filtered,
washed with benzene, and dried under vacuum to give complex 3 as a dark red prism (12.0 mg, 8.6
μmol, 86%). Mp >250 °C. 1H NMR (CDCl3): δ 6.37–6.41 (m, 2H), 6.45–6.49 (m, 2H),
6.55–6.60 (m, 2H), 6.63–6.67 (m, 4H), 6.76–6.87 (m, 10H), 6.92–7.02 (m, 6H), 7.06–7.13 (m, 6H),
7.16–7.21 (m, 4H), 7.28–7.39 (m, 12H), 8.04–8.11 (m, 4H), 8.40–8.43 (m, 2H), 8.85–8.88 (m, 2H).
31P NMR (CDCl3): δ 6.24 (dd, JP-Rh = 146 Hz, JP-P = 396 Hz), 22.74 (dd, JP-Rh = 146 Hz, JP-P = 396
Hz). HRMS (FAB) calcd for C76H56Cl2P4Rh2 [M]+ 1368.0820, found 1368.0819.
4
Me
C
+ BArF–
N
Ph2P
Rh
PPh2
4
A solution of complex 2 (35.0 mg, 50.0 μmol) and NaBArF (44.3 mg, 50.0 μmol) in dry CH3CN
(3.8 mL) was stirred at room temperature for 30 min, and then the mixture was filtered through
Celite, washed with hexane, and dried under vacuum to give complex 4 as an orange solid (47.2 mg,
30.0 μmol, 60%). Mp 146-148 °C. 1H NMR (CD2Cl2): δ 1.79 (s, 3H), 7.43-7.48 (m, 8H),
7.50-7.56 (m, 8H), 7.58 (s, 4H), 7.63–7.68 (m, 10H), 7.75 (s, 8H), 8.11 (d, J = 7.6 Hz, 2H). 13C
NMR (CD2Cl2) for characteristic peaks: δ 99.2 (alkyne, d, J = 9.3 Hz). 31P NMR (CD2Cl2): δ 53.2
(d, JRh-P = 116 Hz). MALDI-TOF-MS (DIT): m/z 690.3 ([M–BArF]+, C40H31NP2Rh, calcd. 690.1);
863.5 ([BArF]–, C32H12BF24, calcd. 863.1). HRMS (FAB) calcd for C40H31NP2Rh [M–BArF]+
690.0987, found 690.0988.
5-PF6
–
+ PF6
O
C
Ph2P
Rh
PPh2
5-PF6
A solution of ligand 1 (16.4 mg, 30.0 μmol) and [RhCl(CO)2]2 (5.8 mg, 15.0 μmol) in dry CH2Cl2
(1.0 mL) was stirred at room temperature for 15 min, and then AgPF6 (7.6 mg, 30.0 μmol) was
added to the reaction mixture. After the additional stirring for 1 h, the reaction mixture was
filtered through Celite, and then concentrated by nitrogen flow to give 22.7 mg of complex 5-PF6
S3

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
as a yellow prism (27.6 μmol, 92%).
Mp > 250 °C. 1H NMR (CD2Cl2): δ 7.47–7.54 (m, 8H), 7.55–7.74 (m, 16H), 7.84 (t, J = 7.8 Hz,
2H), 8.22 (d, J = 7.8 Hz, 2H). 13C NMR (CD2Cl2) for characteristic peaks: δ 106.3 (alkyne, d, J =
5.8 Hz). 31P NMR (CD2Cl2): δ –144.2 (sept, JF-P = 715 Hz), 57.2 (d, JRh-P = 104 Hz). IR (nujol):
2016 cm–1 (νC–O). MALDI-TOF-MS (DIT): m/z 677.3 ([M–PF6]+, C39H28OP2Rh, calcd. 677.1).
HRMS (FAB) calcd for C39H28OP2Rh [M–PF6]+ 677.0670, found 677.0666.
5-BArF
+ BArF–
O
C
Ph2P
Rh
PPh2
5-BArF
5-BArF was prepared according to the similar procedure for 5-PF6. Yellow crystal. 96% yield.
Mp 71.2-71.9 °C. 1H NMR (CD2Cl2): δ 7.48–7.51 (m, 8H), 7.57–7.71 (m, 16H), 7.77 (t, J = 7.8
Hz, 2H), 8.37 (d, J = 7.8 Hz, 2H). 13C NMR (CD2Cl2) for characteristic peaks: δ 106.3 (alkyne, d,
J = 5.8 Hz). 31P NMR (CD2Cl2) δ 57.3 (d, JRh-P = 104 Hz). IR (nujol): 2028 cm–1 (νC–O).
MALDI-TOF-MS (DIT): m/z 677.1 ([M–BArF]+, C39H28OP2Rh, calcd. 677.1); 863.3 ([BArF]–,
C32H12BF24, calcd. 863.1). HRMS (FAB) calcd for C39H28OP2Rh [M–BArF]+ 677.0670, found
677.0670.
S4

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
IV. X-ray crystallographic analyses.
Table S1. Crystallographic data of 2
Empirical Formula
Formula Weight
Crystal Color, Habit
Crystal System
Lattice Parameters
a (Å)
b (Å)
c (Å)
β (°)
V (Å3)
C39.50H31Cl4P2Rh
812.34
orange, prism
monoclinic
11.0023(10)
18.907(2)
17.537(2)
105.272(5)
3519.3(6)
P21/c (#4)
4
1.533
1644.00
9.072
MoK (λ = 0.71070 Å)
graphite monochromated
Space Group
Z value
Dcalc (g cm–3)
F000
μ (MoKa) (cm–1)
Radiation
Temperature (°C)
Max 2θ (°)
–129.8
55.0
No. of Reflections Measured
Structure Solution
Refinement
No. Observations (All reflections)
No. Variables
Reflection/Parameter Ratio
Residuals: R1; wR2
Goodness of Fit Indicator
Max Shift/Error in Final Cycle
Maximum peak in Final Diff. Map (e Å–3)
Minimum peak in Final Diff. Map (e Å–3)
Total: 27279
Direct Methods (SIR92)
Full-matrix least-squares on F2
8035
579
13.88
0.0385; 0.0956
1.073
0.001
1.18
–0.63
S5

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
Table S2. Crystallographic data of 3
Empirical Formula
Formula Weight
Crystal Color, Habit
Crystal System
Lattice Parameters
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C82H68Cl2P4Rh2
1526.12
red, prism
triclinic
11.810(4)
12.102(4)
13.653(4)
66.667(9)
72.108(11)
86.21(2)
1701.6(8)
P-1 (#2)
1
1.489
780.00
7.058
MoK (λ = 0.71070 Å)
graphite monochromated
γ (°)
V (Å3)
Space Group
Z value
Dcalc (g cm–3)
F000
μ (MoKa) (cm–1)
Radiation
Temperature (°C)
Max 2θ (°)
–149.8
54.9
No. of Reflections Measured
Structure Solution
Refinement
No. Observations (All reflections)
No. Variables
Reflection/Parameter Ratio
Residuals: R1; wR2
Goodness of Fit Indicator
Max Shift/Error in Final Cycle
Maximum peak in Final Diff. Map (e Å–3)
Minimum peak in Final Diff. Map (e Å–3)
Total: 13769
Direct Methods (SIR92)
Full-matrix least-squares on F2
7462
433
17.23
0.0938; 0.2355
1.121
0.000
2.42
–1.36
S6

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
Table S3. Crystallographic data of 5-PF6
Empirical Formula
Formula Weight
Crystal Color, Habit
Crystal System
Lattice Parameters
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C53H44F6OP3Rh
1006.75
yellow, prism
triclinic
11.129(4)
14.638(5)
15.649(5)
98.691(5)
90.116(3)
112.174(3)
2328.9(12)
P-1 (#2)
2
1.436
1028.00
5.314
MoK (λ = 0.71070 Å)
graphite monochromated
γ (°)
V (Å3)
Space Group
Z value
Dcalc (g cm–3)
F000
μ (MoKa) (cm–1)
Radiation
Temperature (°C)
Max 2θ (°)
–129.8
54.9
No. of Reflections Measured
Structure Solution
Refinement
Total: 27643
Direct Methods (SIR97)
Full-matrix least-squares on F2
No. Observations (All reflections)
No. Variables
Reflection/Parameter Ratio
Residuals: R1; wR2
Goodness of Fit Indicator
Max Shift/Error in Final Cycle
Maximum peak in Final Diff. Map (e Å–3)
Minimum peak in Final Diff. Map (e Å–3)
10611
577
18.39
0.0691; 0.2025
1.231
0.001
3.16
–0.83
S7

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
V. Cartesian atomic coordinates for the optimized structure of complexes 2 and
5+ (LanL2DZ for rhodium and B3LYP/6-31G(d,p) for other atoms).
2
Atom
Rh
Cl
P
C
C
C
C
C
C
C
C
C
C
C
C
C
C
X
Y
Z
-0.1218695
2.2616784
0.0379404
-1.6799858
-2.0797933
-3.4386164
-4.4011504
-4.0166762
-2.6489292
-2.1750112
0.9084326
0.9887456
1.5777688
2.1017726
2.0391600
1.4473253
0.7771664
2.1134001
2.7124169
1.9891860
0.6596538
0.0547700
-1.3342419
-3.7487791
-5.4573028
-4.7615146
-0.9805093
0.0867836
2.4584778
3.7459648
2.6692797
0.6091446
1.6402628
2.5673997
2.4567994
1.4191109
0.0379404
-1.6799858
-2.0797933
-3.4386164
-4.4011504
-0.2297227
-0.6973241
-0.0557087
-0.0653337
-0.1205368
-0.1146633
-0.0535814
-0.0119932
-0.0288209
-0.0423064
-1.3506960
-2.6442002
-3.6738591
-3.4198760
-2.1310573
-1.0987050
1.5323969
1.8026731
2.9972957
3.9425593
3.6867628
2.4880205
-0.1772935
-0.1610881
-0.0488169
0.0202693
2.3051504
4.4185009
4.8750194
3.1930859
1.0849081
-2.8287533
-4.6713810
-4.2213841
-1.9259871
-0.0950553
-0.0557087
-0.0653337
-0.1205368
-0.1146633
-0.0535814
0.0000000
0.0000000
2.3461969
3.0101535
4.3475429
4.6702832
3.6549184
2.3179628
1.9852757
0.6300000
3.3181069
2.7817408
3.5157887
4.7851190
5.3188745
4.5889767
2.9231695
2.5767365
2.9730034
3.7054960
4.0397581
3.6524956
5.1355822
5.7104201
3.9104785
1.5284666
3.9204348
4.6035961
4.0082445
2.6998888
1.9807248
1.7814072
3.0893096
5.3526886
6.3011814
5.0035512
-2.3461969
-3.0101535
-4.3475429
-4.6702832
-3.6549184
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
P
C
C
C
C
S8

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-4.0166762
-0.0119932
-0.0288209
-0.0423064
-1.3506960
-2.6442002
-3.6738591
-3.4198760
-2.1310573
-1.0987050
1.5323969
1.8026731
2.9972957
3.9425593
3.6867628
2.4880205
-0.1772935
-0.1610881
-0.0488169
0.0202693
2.3051504
4.4185009
4.8750194
3.1930859
1.0849081
-2.8287533
-4.6713810
-4.2213841
-1.9259871
-0.0950553
-2.3179628
-1.9852757
-0.6300000
-3.3181069
-2.7817408
-3.5157887
-4.7851190
-5.3188745
-4.5889767
-2.9231695
-2.5767365
-2.9730034
-3.7054960
-4.0397581
-3.6524956
-5.1355822
-5.7104201
-3.9104785
-1.5284666
-3.9204348
-4.6035961
-4.0082445
-2.6998888
-1.9807248
-1.7814072
-3.0893096
-5.3526886
-6.3011814
-5.0035512
-2.6489292
-2.1750112
0.9084326
0.9887456
1.5777688
2.1017726
2.0391600
1.4473253
0.7771664
2.1134001
2.7124169
1.9891860
0.6596538
0.0547700
-1.3342419
-3.7487791
-5.4573028
-4.7615146
-0.9805093
0.0867836
2.4584778
3.7459648
2.6692797
0.6091446
1.6402628
2.5673997
2.4567994
1.4191109
S9

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5+
Atom
Rh
P
X
Y
Z
0.0412229
-0.0549100
-0.0549100
-2.9687920
-1.8220903
2.2408161
2.6436163
1.6605972
2.0304258
3.3787620
4.3587041
4.0018476
-1.0315497
-1.1410852
-1.8144938
-2.3891072
-2.2883200
-1.6118170
-0.6677626
0.2144767
-0.2742641
-1.6417514
-2.5256059
-2.0441245
5.4061410
1.2719424
-1.5504882
4.7599424
-1.8961604
-0.7005797
1.2803569
3.6664523
-2.9191087
-2.7441890
-2.0192784
-2.7394318
-3.5914664
0.4172548
2.2408161
2.6436163
1.6605972
2.0304258
3.3787620
4.3587041
4.0018476
-0.2014839
-0.0465604
-0.0465604
-0.4511775
-0.3385432
-0.2398490
-0.2641265
-0.1988074
-0.2561288
-0.3632828
-0.4141497
-0.3661617
-1.3096547
-2.5925957
-3.6030021
-3.3399608
-2.0648351
-1.0506320
1.5878961
2.5927391
3.8520380
4.1196811
3.1242756
1.8667653
-0.4986146
-0.2239742
-0.0594961
-0.4148151
-4.5922863
-2.7964078
2.3983061
-0.4098861
-4.1256166
1.1032797
5.0992736
-1.8563912
3.3262019
4.6213052
-0.2398490
-0.2641265
-0.1988074
-0.2561288
-0.3632828
-0.4141497
-0.3661617
0.0000000
2.3818488
-2.3818488
0.0000000
0.0000000
0.6225216
2.0010843
3.0065621
4.3526676
4.6978591
3.6998728
2.3551811
3.2776309
2.7172072
3.4031202
4.6487392
5.2093367
4.5302231
2.9433189
3.3678988
3.7217722
3.6545498
3.2286823
2.8692726
3.9732052
5.1289838
4.9690127
1.5802358
2.9624187
1.7445810
3.4282824
5.7437145
5.1792718
2.5417346
3.9327513
6.1751106
3.1760282
4.0529524
-0.6225216
-2.0010843
-3.0065621
-4.3526676
-4.6978591
-3.6998728
-2.3551811
P
O
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
C
C
C
C
C
C
C
S10

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-1.0315497
-1.3096547
-2.5925957
-3.6030021
-3.3399608
-2.0648351
-1.0506320
1.5878961
2.5927391
3.8520380
4.1196811
3.1242756
1.8667653
-0.4986146
-0.2239742
-0.0594961
-0.4148151
-4.5922863
-2.7964078
2.3983061
-0.4098861
-4.1256166
1.1032797
5.0992736
-1.8563912
3.3262019
4.6213052
-3.2776309
-2.7172072
-3.4031202
-4.6487392
-5.2093367
-4.5302231
-2.9433189
-3.3678988
-3.7217722
-3.6545498
-3.2286823
-2.8692726
-3.9732052
-5.1289838
-4.9690127
-1.5802358
-2.9624187
-1.7445810
-3.4282824
-5.7437145
-5.1792718
-2.5417346
-3.9327513
-6.1751106
-3.1760282
-4.0529524
-1.1410852
-1.8144938
-2.3891072
-2.2883200
-1.6118170
-0.6677626
0.2144767
-0.2742641
-1.6417514
-2.5256059
-2.0441245
5.4061410
1.2719424
-1.5504882
4.7599424
-1.8961604
-0.7005797
1.2803569
3.6664523
-2.9191087
-2.7441890
-2.0192784
-2.7394318
-3.5914664
0.4172548
S11

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
2

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
2

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
2

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
3

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
3

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
4

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
4

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
4

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5-BArF

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5-BArF

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5-BArF

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5-PF6

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5-PF6

Electronic Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2012
5-PF6