Supporting Information

 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2012

Aerobic Oxidation of Carbon Monoxide in a Tetrametallic Complex

Cristina Tejel,* Sofa Sancho, Jos A. Lpez, and Miguel A. Ciriano[a]

chem_201202834_sm_miscellaneous_information.pdf
 S1

Supporting information belonging to the paper:

Aerobic Oxidation of Carbon Monoxide in a Tetrametallic Complex

Cristina Tejel*, Sofía Sancho, José A. López, and Miguel A. Ciriano

Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-
Universidad de Zaragoza, Pedro Cerbuna 12, Zaragoza 50009, Spain

Index Page

Experimental details S2-S5

X-ray diffraction and DFT studies S5-S6
Selected NMR spectra S7-S10
Selected IR spectra S11
Selected HRMS spectra S12
Structure (ORTEP) of complexes 2B, 3 and 4 S13-S14
Selected bond distances and angles of complexes 2B, 3 and 4 S15-S16
DFT results S17-S28
References S29
 S2

General methods.

All syntheses were performed under an argon atmosphere, using standard Schlenk techniques. Solvents were
dried and distilled under argon before use by standard methods. The complexes [{Rh(CO)2(-Cl)}2],[S1]
[{Rh(cod)(-Cl}2],[S2] and [{Ir(cod)(-Cl}2][S3] and the organic 1,8-naphthyridine-2,7-dione [(HO)2napy][S4] were
prepared according to literature methods. All other chemicals are commercially available and were used
without further purification. Elemental analyses were performed using a Perkin-Elmer 2400 microanalyzer.
Mass spectra of complexes 2 and 4 were obtained on a MicroToF-Q spectrometer equipped with a HPLC
injector and ESI+ (NCMe/H2O 7:3) while complex 3 was adquired on a Esquire3000 plus (ESI+) in methanol.
NMR experiments were carried out on Bruker AV 500 and AV 400 instruments operating at 500 and 400 MHz
for 1H, respectively. Chemical shifts are reported in parts per million and referenced to SiMe4, using the
internal signal of the deuterated solvent as a reference. For [O2napy]2 and cod ligands numbering scheme
see Figures S5-S8. IR spectra in solution were recorded with a Nicolet 550 spectrophotometer using NaCl
cells, while IR spectra of solid samples were recorded with a Perkin-Elmer 100 FT-IR spectrometer (4000−400
cm−1) equipped with an ATR (attenuated total reflectance) accessory. UV-Vis spectra were recorded on a
Thermo Scientific Evolution 600 UV-Visible spectrophotometer on dichloromethane solutions. Gas
chromatography/mass spectra (GC/MS) was carried out on an Agilent 6890 Series GC System chromatograh
equipped with EI for ionization.

Synthesis of the complexes.

K2[{Rh(CO)2(-O2napy)}2] (K2[1]). Solid [{Rh(CO)2(-Cl)}2] (97.2 mg, 0.25 mmol) was added to a suspension
of K2[O2napy] in methanol (5 mL) at 0 ºC, prepared ‘in situ’ by reacting (HO)2napy (81.1 mg, 0.50 mmol) and
KOH/MeOH (0.49 M, 1.0 mmol, 2.04 mL). The resulting purple solution was stirred for 30 min and then filtered
over celite. The filtrate was concentrated to ca. 2 mL and further addition of diethyl ether produced the
crystallization of the complex. The purple solid was filtered, washed with diethyl ether (2 x 3 mL) and vacuum-
dried. Yield: 171.3 mg (91.3 %). 1H NMR (500.13 MHz, [D4]-methanol, 25 ºC, TMS):  = 7.26 (d, 3J(H,H) = 8.6
Hz, 4H; H4), 6.01 (d, 3J(H,H) = 8.6 Hz, 4H; H3);13C{1H}-apt NMR (125.75 MHz, [D4]-methanol, 25 ºC, TMS):  =
188.8 (d, J(C,Rh) = 67 Hz; RhCO), 173.3 (C2), 161.4 (C8’), 138.9 (C4), 112.0 (C3), 108.9 (C4’); IR (ATR):  =
2068 (s), 2041 (w), 1989 (s) cm–1 (CO), 1615, 1598 cm–1 (O2napy), 3200, 1651 cm–1 (H2O); elemental
analysis calcd (%) for C20H8N4K2O8Rh2▪2H2O (752.35): C 31.93, H 1.61, N 7.45; found: C 31.96, H 1.67, N
7.52.
The labeled compound K2[{Rh(13CO)2(-O2napy)}2] (K2[1*]) was prepared as follows: solid [{Rh(cod)(-Cl}2]
(15.0 mg, 0.030 mmol) was added to a solution of K2[O2napy] (0.060 mmol) in [D4]-methanol (0.5 mL)
13
prepared ‘in situ’ as above in a NMR tube. The resulting suspension was treated with CO to produce a
purple solution whose RMN data were found to be similar to those of K2[1].

[{RhIr(cod)(CO)2(-O2napy)}2] (2). A solution of [{Ir(cod)(-Cl}2] (167.9 mg, 0.25 mmol) in dichlorometane (3

mL) was added at 0 ºC to a methanolic solution of K2[1] (0.25 mmol) prepared as described above. The blue
solution formed initially evolved eventually to a dark-blue suspension overnight. The resulting suspension was
evaporated to dryness and the residue was extracted with dichloromethane and filtered over celite. The
 S3

solution was concentrated to ca. 2 mL and carefully layered with hexane (8 mL). The blue microcrystals
deposited in three days at 0 ºC were decanted, washed with cold hexane (2 x 3 mL) and vacuum-dried. Yield:
263.3 mg (85%). 1H NMR (500.13 MHz, CDCl3, 25 ºC, TMS):  = 7.26 (d, 3J(H,H) = 8.7Hz, 4H; H4), 6.46 (d,
3
J(H,H) = 8.7Hz, 4H; H3), 4.40 (br s, 4H) and 4.22 (br s, 4H; =CH), 2.58 (br s, 4H) and 2.55 (br s, 4H; CH2exo),
1.93 (br s, 4H) and 1.79 (br s, 4H; CH2endo); 13C{1H}-apt NMR (125.75 MHz, CDCl3, 25 ºC, TMS):  = 190.4 (d,
J(C,Rh) = 62Hz; RhCO), 172.1 (C2), 155.1 (C8’), 137.5 (C4), 114.0 (C3), 110.9 (C4’), 69.4 and 63.8 (=CH),
32.3 and 31.8 (CH2); IR (CH2Cl2):  = 2084 (vs), 2078 (sh), 2060 (w), 2032 (s), 2023 (s), 1998 (m), 1824 (m)
cm–1 (CO), 1622, 1614, 1599 cm–1 (O2napy); IR (ATR):  = 2076 (vs), 2015 (s), 1984 (vs), 1807 (vs) cm–1
(CO), 1620, 1613, 1597 cm–1 (O2napy); UV/Vis (CH2Cl2):  () = 629 (9734), 350 (24287), 230 nm (41002 mol–
1
dm3 cm–1); MS (ESI+): m/z (%):1239.9547 (2) [M+] (calc. for [M+]: 1239.9584); elemental analysis calcd (%)
for C36H32N4O8Ir2Rh2 (1239.95): C 34.87, H 2.60, N 4.52; found: C 34.78, H 2.56, N 4.51.

The labeled compound [{RhIr(cod)(13CO)2(-O2napy)}2] (2*) was prepared following an identical procedure
starting from K2[1*]. IR (ATR):  = 2028 (s), 1970 (s), 1939 (s), 1766 (s) cm–1 (CO), 1620, 1613, 1597 cm–1
(O2napy).

[{Rh2(cod)(CO)2(-O2napy)}2] (3) was prepared as described above for complex 2 starting from (HO)2napy
(81.1 mg, 0.50 mmol), KOH/MeOH (0.49 M, 1.0 mmol, 2.04 mL), [{Rh(CO)2(-Cl)}2] (97.2 mg, 0.25 mmol) and
[{Rh(cod)(-Cl}2] (123.3 mg, 0.25 mmol) and isolated as an emerald green solid. Yield: 236.1 mg (89%). 1H
NMR (500.13 MHz, CD2Cl2, –40 ºC, TMS):  = 7.23 (d, 3J(H,H) = 8.6 Hz, 4H; H4), 6.18 (d, 3J(H,H) = 8.6 Hz,
4H; H3), 4.15 (br s, 4H) and 3.84 (br s, 4H; =CH), 2.70 (br s, 4H) and 2.50 (br s, 4H; CH2exo), 1.85 (m, 4H) and
13
1.69 (m, 4H; CH2endo); C{1H}-apt NMR (125.75 MHz, CD2Cl2, –40 ºC, TMS):  = 187.2 (d, J(C,Rh) = 66 Hz;
RhCO), 173.4 (C2), 156.5 (C8’), 137.8 (C4), 113.8 (C3), 110.1 (C4’), 79.8 (d, J(C,Rh) = 20 Hz) and 69.0 (d,
J(C,Rh) = 18 Hz; =CH), 30.9 and 30.5 (CH2); IR (CH2Cl2):  = 2083 (s), 2057 (w), 2021 (s) cm–1 (CO), 1619,
1598 cm–1 (O2napy); IR (ATR):  = 2075 (s), 2057 (s), 2011 (vs), 2003 (vs), 1976 (sh) cm–1 (CO), 1615, 1596
cm–1 (O2napy); UV/Vis (CH2Cl2):  () = 672 (14171), 347 (31809), 231 nm (50261 mol–1 dm3 cm–1); MS
(ESI+): m/z (%): 1060.9 (84) [M+]; elemental analysis calcd (%) for C36H32N4O8Rh4 (1060.30): C 40.78, H 3.04,
N 5.28; found: C 40.63, H 2.74, N 5.26.
The labeled compound [{Rh2(cod)(13CO)2(-O2napy)}2] (3*) was prepared following an identical procedure
starting from K2[1*]. IR (CH2Cl2):  = 2034 (s), 2009 (w), 1975 (s) cm–1 (CO), 1617, 1599 cm–1 (O2napy).

[{RhIr(cod)(CO)(-O2napy)}2(-CO2-2-C,O)] (4). A suspension of 2 (88.0 mg, 0.071 mmol) in

dichlorometane (6 mL) was shaken under an oxygen atmosphere for 36 h. The reaction was monitored by IR
spectroscopy to ensure the disappearance of the starting material. The suspension was evaporated to
dryness and the solid was washed with methanol (1 x 5 mL) and diethyl ether (3 x 5 mL) and vacuum-dried.
Yield: 76.8 mg (88%). 1H NMR (500.13 MHz, CDCl3, 25 ºC, TMS):  = 7.35 (d, 3J(H,H) = 8.4, 1H, H5A), 7.31 (d,
J(H,H) = 8.6, 1H, H4A), 6.54 (d, 3J(H,H) = 8.6, 1H, H3A), 6.40 (d, 3J(H,H) = 8.4, 1H, H6A) (O2napy A), 7.35 (d,
3

J(H,H) = 8.4, 1H, H5B), 7.34 (d, 3J(H,H) = 8.4, 1H, H4B), 6.44 (d, 3J(H,H) = 8.7, 1H, H3B), 6.40 (d, 3J(H,H) =
3

8.6, 1H, H6B) (O2napy B), 5.49 (t, 3J(H,H) = 6.8Hz, 1H, H1), 4.83 (m, 1H, H5), 4.74 (dd, 3J(H,H) = 14.4, 1J(H,H)
= 7.3Hz, 1H, H2), 4.67 (m, 1H, H6), 3.02 (m, 1H, CH28a), 2.82 (m, 1H, CH28b), 2.81 (m, 1H, CH24a), 2.69 (m, 1H,
 S4

CH27a), 2.38 (m, 1H, CH23a), 2.05 (m, 1H, CH24b), 1.79 (m, 1H, CH23b) and 1.61 (m, 1H, CH27b) (cod 1); 5.00 (t,
J(H,H) = 6.8, 1H, H1), 4.68 (m, 1H, H5), 4.65 (m, 1H, H2), 4.35 (dd, 3J(H,H) = 13.4, 1J(H,H) = 7.3Hz 1H, H6),
3

2.79 (m, 1H, CH28a), 2.78 (m, 1H, CH24a), 2.63 (m, 1H, CH23a), 2.40 (m, 1H, CH27a), 2.28 (m, 1H, CH24b), 2.10
(m, 1H, CH28b), 1.76 (m, 1H, CH23b) and 1.73 (m, 1H, CH27b) (cod 2); chemical shifts for carbons were
13
obtained from C,1H-hsqc and 13
C,1H-hmbc spectra (125.75 MHz, CDCl3, 25 ºC, TMS):  = 171.0(C2,7A),
156.4 (C8’A), 137.7 (C5A), 137.3(C4A), 114.6 (C3A), 113.0 (C6A), 112.1 (C4’A) (O2napy A), 172.6 (C2,7B), 153.5
(C8’B), 137.7 (C4,5B), 114.8 (C6B), 114.5 (C3B), 110.8 (C4’B) (O2napy b), 82.3 (C5), 77.8 (C1), 73.9 (C2), 69.1 (C6)
36.4 (C8), 31.5 (C4), 31.2 (C7), 28.6 (C3) (cod 1), 78.6 (C1), 73.1 (C5), 69.6 (C6), 67.9 (C2), 34.8 (C4), 32.0 (C8),
31.3 (C3), 28.5 (C7) (cod 2); IR (CHCl3):  = 2048 (s), 2009 (w), cm–1 (CO), 1622, 1615, 1600 cm–1 (O2napy);
1610 cm–1 (-CO2); UV/Vis (CH2Cl2):  () = 599 (8235), 535 (8235), 343 (25588), 236 (32941 mol–1 dm3 cm–
1
); MS (ESI+): m/z (%):1228.9673 (100) [M+H+] (calc. for [M+H+]: 1228.9662); elemental analysis calcd (%) for
C35H32N4O8Rh2Ir2 (1227.95): C 34.25, H 2.60, N 4.60; found: C 33.71, H 2.91, N 4.23.

The labeled compound [{RhIr(cod)(13CO)(-O2napy)}2(-13CO2-2-C,O)] (4*) was prepared in a NMR tube

starting from 2*. IR (CHCl3):  = 2001 (s), 1963 (w), cm–1 (CO), 1623, 1616, 1600 cm–1 (O2napy); 1574 cm–1
13
(-CO2); C{1H} NMR (125.75 MHz, CD2Cl2, 25 ºC, TMS):  = 192.8 (dd, J(C,Rh) = 70 Hz; J(C,C) = 4 Hz,
RhCO), 188.4 (dd, J(C,Rh) = 63 Hz; J(C,C) = 2 Hz, RhCO), 173.4 (dm, J(C,Rh) = 25 Hz; Rh-(-CO2)).
The labeled compound [{RhIr(cod)(CO)(-O2napy)}2(-CO2-2-C,18O)] (4**) was prepared in a NMR tube
18
shaking a suspension of complex 4 (19.0 mg) in CD2Cl2 (0.5 mL) under na atmosphere of O2 for 24h. A
18
sample of the gaseous phase was injected in the GC/MS in which the masses of O2 (m/z: 36), CO[18O] (m/z:
46), and CD2Cl2 (m/z: 87) were observed.The suspension was centrifuged and the solid was washed with
methanol, diethyl ether and vacuum-dried. MS (ESI+): m/z (%):1230.9704 (100) [M+H+] (calc. for [M+H+]:
1230.9652)
 S5

Uptake of oxygen.

A 15 mL thick-walled flask was filled with a solution of 2 (61.9 mg, 0.05 mmol) in CH2Cl2 (6 mL), connected to
a device to measure the pressure and to a reservoir to provide extra oxygen if necessary. After pressuring the
reactor with oxygen to 1.58 bar, the flask was shaken at 20 ºC and the pressure was measured for 12 h.
Figure S1 shows the pressure of the reactor and reservoir versus time.

10
Reservoir
9
8
7
6
P (bar)

5
4
3
Reactor
2
1
0
0 100 200 300 400 500 600 700

t (min)

Figure S1.

X-ray diffraction studies on complexes 2B, 3 and 4·2(CH2Cl2).

Intensity measurements for 2, 3 and 4·2(CH2Cl2) were collected with a Bruker Smart Apex diffractometer,
using  scans of 0.3º, at 100 K (2, 3) and 150 K (4·2(CH2Cl2)), with graphite-monochromated MoK radiation.
A semi-empirical absorption correction was applied to each data set with the multi-scan method.[S5] The
structures were solved by direct methods and refined by full-matrix least-squares, with the program
SHELX97[S6] in the WINGX[S7] package. All non-hydrogen atoms were refined with anisotropic displacement
parameters, except those involved in disorder. Hydrogen atoms were positioned geometrically, except those
bonded to olefinic carbons of the cod ligands that were found in difference-fourier maps, and refined by the
riding mode.
 S6

Table S1. Selected crystal, measurement and refinement data for compounds 2B, 3 and 4·2(CH2Cl2).

2B 3 4·2(CH2Cl2)
Formula C36H32Ir2N4O8Rh2 C36H32N4O8Rh4 C35H33Ir2N4O8Rh2·2(CH2Cl2)
formula weight 1233.88 1060.30 1396.72
Colour navy blue emerald green dark blue
crystal system Monoclinic Monoclinic Monoclinic
space group P21/n P21/n P21/c
a[Å] 14.3516(11) 18.5764(17) 12.2002(7)
b[Å] 12.2882(9) 16.0192(14) 20.9028(13)
c[Å] 19.5210(14) 23.313(2) 15.5043(9)
[º] 90 90 90
[º] 104.5334(9) 96.003(2) 102.137(1)
[º] 90 90 90
3
V[Å ] 3332.5(4) 6899.6(11) 3865.5(4)
Z 4 8 4
F(000) 2336 4160 2648
calcd[g cm-3] 2.469 2.041 2.400
 [mm-1] 8.997 1.940 8.038
crystal size[mm] 0.38 × 0.14 × 0.01 0.18 × 0.14 × 0.10 0.29 × 0.11 × 0.07
temperature [K] 100(2) 100(2) 150(2)
 limits [º] 28.39 26.00 28.51
collected reflns. 38521 39420 43856
unique reflns. (Rint) 7634 (0.0459) 13522 (0.0612) 9190 (0.0351)
reflns. with I>2(I) 6138 9707 7736
parameters/restraints 469/0 931/0 505/5
R1 (on F, I>2(I)) 0.0328 0.0483 0.0323
2
wR2 (on F , all data) 0.0813 0.1014 0.0843
max./min.  [e Å-3] 2.594/-1.260 1.379/-1.605 2.432/-2.087
goodness of fit 1.038 1.022 1.046

DFT optimization of complexes 2A, 2B, B, C, and 4.

The computational method used was density functional theory (DFT) with the B3LYP exchange correlation
functional,[S8] using the Gaussian 09[S9] program package. The basis sets used for the full optimization of the
structure were a LanL2DZ effective core potential for the metal atoms and 6-31G(d,p) for the remaining
atoms.
 S7

Selected NMR spectra

Rh-13CO

4 2
4'
3

8' 2
O N N O
O N N O
Rh Rh = CO

4 3
4 3
4’
3 110
120
4
130
4 140 8’
2
7.0 6.5 6.0 5.5

2 8’ 4 3 4’

Figure S2. 13C{1H}-apt NMR spectrum of K2[{Rh(13CO)2(-O2napy)}2] (K2[1*]) in [D4]-methanol. The insets
show selected regions from the 1H,13C-hsqc (left) and 1H,13C-hmbc (right) spectra. The red circle denotes free
cod.
 S8

4
4'
3

8' 2
O N N O
O N N O
Rh
Rh Rh Rh = CO

4 3

CH2

2 4’
8’
Rh-CO 4 3

=CH =CH

Figure S3. 1H (top) and 13C{1H}-apt (bottom) NMR spectra of complex 3 in CD2Cl2. The black circles denote
hexane.
 S9

4
4'
3

8' 2
O N N O
O N N O
Ir Rh Rh Ir = CO
4
3

CH2 CH2

2 4’
Rh-CO 8’
4 3

=CH =CH

Figure S4. 1H (top) and 13C{1H}-apt (bottom) NMR spectra of complex 2 in CDCl3. The asterisk (*) denotes
dichloromethane and the black circles denote hexane.
 S10

5 4
4'
6 3
7 8 1
8' 2
O N N O 7
6
O N N O 3
2
Ir
Rh Rh
Ir = CO 4
5
O C
O

O2napy =CH
* - CH2

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

Rh-CO
Rh-CO CO2
Rh-CO2-Rh

128 124

Figure S5. 1H (top) and 13C{1H} (bottom) NMR spectra of complex 4* in [D4]-methanol, showing the CO2
released. The asterisk (*) denotes methanol.
 S11

Selected regions of IR spectra

3 (CH2Cl2)

2 (CH2Cl2)

2 (solid)

2150 2100 2050 2000 1950 1900 1850 1800 1750 1700 cm1

Figure S6. IR spectra of complexes 2 and 3 in dichlorometane (complex 3 in red, complex 2 in blue) and of
complex 2 in the solid state (in purple).

4 (CHCl3)

4* (CHCl3)

2100 2050 2000 1950 1900 1850 1800 1750 1700 1650 1600 1550 cm1

Figure S7. IR spectra of complexes 4 and 4* in chloroform.

 S12

Selected HRMS spectra

Intens. 2. 1226.9644 +MS, 0.8-1.3min #(49-80), -Peak Bkgrnd

x104
1228.9673

2 1224.9610

0
x104 2. C 35 H 33 Ir 2 N 4 O 8 Rh 2 ,1228.97
1226.9639
1228.9662
6

2 1224.9615

0
1222 1224 1226 1228 1230 1232 1234 1236 m/z

Meas. m/z Formula m/z err [mDa] err [ppm] mSigma

1228.9673 C 35 H 33 Ir 2 N 4 O 8 Rh 2  1228.9662 ‐1.0 ‐0.8 46.2

Figure S8. HRMS of complex [{RhIr(cod)(CO)(-O2napy)}2(-CO2-2-C,O)] (4).

Intens. 2. +MS, 0.9-1.2min #(52-72), -Peak Bkgrnd

x104
1228.9622

2.5

1230.9652
2.0

1.5

1226.9577

1.0
1229.9661

0.5 1231.9696
1227.9624
1232.9714
1224.9603

0.0
1224 1226 1228 1230 1232 1234 m/z

Meas. m/z Formula m/z err [mDa] err [ppm]

1230.9652 C 35 H 33 Ir 2 N 4 O 7 18O Rh 2  1230.9704 ‐5.2 ‐4.2

Figure S9. HRMS of complex [{RhIr(cod)(CO)(-O2napy)}2(-CO2-2-C,18O)] (4**).

 S13

Figure S10. Structure (ORTEP at 50% level) of the bridging carbonyl heterometallic complex
[{RhIr(cod)(CO)2(-O2napy)}2] (2B).

Figure S11. Structure (ORTEP at 50% level) of CO2 bridged complex [{RhIr(cod)(CO)(-O2napy)}2(-CO2-2-
C,O)] (4).
 S14

Figure S12. Structure (ORTEP at 50% level) of the two independent molecules of the tetranuclear complex
[{Rh2(cod)(CO)2(-O2napy)}2] (3).
 S15

Table S2. Selected bond distances (Å) and angles (º) for complexes 2B and 3.

2B (M = Ir) 3b (M = Rh)

M1-Rh2 2.5838(5) 2.9435(8) [2.9612(8)]

Rh2–Rh3 2.6779(6) 2.7947(8) [2.7982(8)]
Rh3–M4 2.8683(5) 2.9164(8) [2.9293(8)]
M1–O1 2.050(4) 2.164(5) [2.108(4)]
M1–O3 2.278(4) 2.126(5) [2.118(4)]
a
M1–Ct1 2.046(6) 1.980(8) [1.982(8)]
M1–Ct2a 1.973(6) 1.991(7) [1.971(7)]
M1-C35 2.080(6) -
Rh2–N1 2.147(5) 2.124(5) [2.127(5)]
Rh2–N3 2.213(5) 2.112(5) [2.099(5)]
Rh2–C33 1.810(6) 1.868(7) [1.850(8)]
Rh2–C35 1.998(6) 1.872(8) [1.862(7)]
Rh3–N2 2.096(4) 2.109(5) [2.105(5)]
Rh3–N4 2.110(5) 2.080(6) [2.119(5)]
Rh3–C34 1.871(6) 1.845(7) [1.878(8)]
Rh3–C36 1.863(6) 1.848(8) [1.855(7)]
M4–O2 2.052(4) 2.092(5) [2.112(5)]
M4–O4 2.055(4) 2.109(5) [2.100(4)]
a
M4–Ct3 1.980(6) 1.985(7) [1.994(7)]
M4–Ct4a 1.986(6) 1.982(7) [1.976(8)]
C17–C18 1.406(9) 1.382(10) [1.417(10)]
C21–C22 1.447(9) 1.395(10) [1.414(10)]
C25–C26 1.399(9) 1.412(10) [1.434(9)]
C29–C30 1.400(9) 1.409(10) [1.407(10)]
M1–Rh2–Rh3 172.40(2) 166.51(3) [166.37(3)]
Rh2–Rh3–M4 173.90(2) 167.61(3) [168.55(3)]
O1–M1–Ct1 170.34(2) 168.0(3) [171.2(3)]
O3–M1–Ct2 116.69(2) 171.4(3) [170.5(2)]
O3–M1–C35 127.06(2) -
Ct2–M1–C35 114.99(2) -
a) Ct1, Ct2, Ct3 and Ct4 are the middle points of the C17-C18, C21-C22, C25-C26 and C29-C30 olefinic
bonds, respectively. b) The data of the second independent molecule are in brackets.
 S16

Table S3. Selected experimental (X-ray) and calculated (DFT optimized) bond distances (Å) and angles (º) for
complex 4.

Experimental Calculated

Ir1-Rh2 2.7827(5) 2.906

Rh2–Rh3 2.4931(6) 2.529
Rh3–Ir4 2.7763(5) 2.849
Ir1–O1 2.029(4) 2.065
Ir1–O3 2.056(4) 2.089
a
Ir1–Ct1 2.008(6) 2.036
a
Ir1–Ct2 1.997(6) 2.027
Rh2–N1 2.106(4) 2.139
Rh2–N3 2.154(4) 2.110
Rh2–C33 1.840(6) 1.869
Rh2–O8 1.968(7) [1.976(6)] 2.103
Rh3–N2 2.101(4) 2.157
Rh3–N4 2.107(4) 2.326
Rh3–C34 1.840(6) 1.858
Rh3–C35 2.130(8) [2.117(8)] 2.082
Ir4–O2 2.038(4) 2.054
Ir4–O4 2.042(4) 2.104
a
Ir4–Ct3 2.001(7) 2.044
Ir4–Ct4a 2.005(7) 2.037
C35–O7 1.249(10) [1.243(9)] 1.214
C35–O8 1.351(11) [1.344(10)] 1.301
Ir1–Rh2–Rh3 173.38(2) 175.83
Rh2–Rh3–Ir4 175.79(2) 167.56
O7–C35–O8 119.7(9) [124.2(8)] 128.86
a) Ct1, Ct2, Ct3 and Ct4 are the middle points of the C17-C18, C21-C22, C25-C26 and C20-C30 olefinic
bonds, respectively.
 S17

DFT results

Figure S13. LUMO (top) and HOMO (bottom) for complex 4 from DFT calculations.
 S18

0
2A + O2
‐10
B, ‐10.53
‐20

‐30
H (kcal/mol)

‐40

‐50 (C + CO2), ‐46.87

‐60

‐70

‐80

‐90
(4 + CO2), ‐90.60

Figure S14. Energy profile for the reaction 2A + O2  4 + CO2. The bridging carbonyl isomer 2B was found to
be 4.01 kcal.mol1 higher in energy (H) than the ‘all terminal’ carbonyls (2A).
 S19

Figure S15. Optimized geometry of complex [{RhIr(cod)(CO)(-O2napy)}2(-CO2-2-C,O)] (4).

Table S4. Coordinates (xyz-coordinates) for the optimized geometry of complex [{RhIr(cod)(CO)(-
O2napy)}2(-CO2-2-C,O)] (4).
---------------------------------------------------------
Center Coordinates (Angstroms)
Number Element X Y Z
---------------------------------------------------------
1 Ir -4.145367 -0.057913 -0.050055
2 Rh -1.251820 -0.326305 -0.070184
3 Rh 1.270491 -0.455532 0.063612
4 Ir 4.084268 -0.009826 0.038868
5 O -3.464199 1.434341 1.203558
6 O 3.451334 0.979017 1.724224
7 O -3.540622 1.017608 -1.735456
8 O 3.412253 1.495403 -1.269247
9 N -1.170547 1.231811 1.393053
10 N 1.154544 1.086931 1.566318
11 N -1.243110 1.194414 -1.533041
12 N 1.116587 1.326277 -1.423301
13 C -2.352286 1.804370 1.732812
14 C -2.408918 2.857111 2.704432
15 H -3.382764 3.271154 2.933415
16 C -1.260932 3.281492 3.301008
17 H -1.278972 4.070983 4.047763
18 C -0.019075 2.697302 2.950496
19 C -0.011340 1.666943 1.970780
20 C 1.215866 3.094042 3.517907
21 H 1.220736 3.873500 4.275278
22 C 2.376035 2.508516 3.107905
23 H 3.347285 2.778483 3.502737
24 C 2.330103 1.497832 2.096196
25 C -2.434976 1.608867 -2.038916
26 C -2.488382 2.704643 -2.959348
27 H -3.462911 2.996691 -3.329893
28 C -1.336606 3.342240 -3.316704
29 H -1.360589 4.186918 -4.000703
30 C -0.088990 2.913768 -2.802108
 S20

31 C -0.060220 1.803895 -1.911178

32 C 1.145959 3.533264 -3.127388
33 H 1.140301 4.386927 -3.800475
34 C 2.315393 3.069041 -2.602005
35 H 3.275475 3.520218 -2.820759
36 C 2.286663 1.927430 -1.729995
37 C -4.615389 -1.845729 -1.196083
38 H -3.985673 -1.872568 -2.080014
39 C -5.688381 -0.924497 -1.246841
40 H -5.762417 -0.319852 -2.151029
41 C -6.970277 -1.003483 -0.434384
42 H -7.657880 -1.736006 -0.882433
43 H -7.467951 -0.030335 -0.512302
44 C -6.722288 -1.327667 1.056573
45 H -6.737980 -2.409446 1.221797
46 H -7.542099 -0.918845 1.655690
47 C -5.398642 -0.748497 1.554259
48 H -5.480416 0.076384 2.260459
49 C -4.179120 -1.472713 1.561600
50 H -3.424324 -1.166190 2.284211
51 C -4.002633 -2.893049 1.056678
52 H -4.428773 -3.605009 1.778662
53 H -2.927524 -3.090469 1.032169
54 C -4.610966 -3.117596 -0.348253
55 H -5.631785 -3.506423 -0.270673
56 H -4.035691 -3.888359 -0.870619
57 C 5.548704 -0.427522 -1.464176
58 H 5.498124 0.388916 -2.183574
59 C 4.547001 -1.419935 -1.563830
60 H 3.825549 -1.281819 -2.364806
61 C 4.720446 -2.856818 -1.071083
62 H 5.770296 -3.148838 -1.178521
63 H 4.152555 -3.524937 -1.724623
64 C 4.248372 -3.051056 0.389436
65 H 4.809770 -3.866612 0.868286
66 H 3.200125 -3.359155 0.408793
67 C 4.356132 -1.792522 1.228244
68 H 3.634130 -1.740629 2.040415
69 C 5.515333 -0.986718 1.317441
70 H 5.602588 -0.351065 2.197235
71 C 6.820612 -1.297342 0.585894
72 H 6.928213 -2.380198 0.469680
73 H 7.664102 -0.974023 1.204005
74 C 6.901848 -0.594484 -0.790239
75 H 7.592846 -1.130713 -1.457343
76 H 7.325160 0.407407 -0.656310
77 C -1.413135 -1.655724 -1.373434
78 O -1.554174 -2.454935 -2.187035
79 C 1.446531 -1.849614 -1.152252
80 O 1.590321 -2.704811 -1.913416
81 C 0.537555 -1.768995 1.502456
82 O -0.759930 -1.700240 1.444137
83 O 1.232847 -2.415681 2.258739
---------------------------------------------------------
 S21

Figure S16. Optimized geometry of complex [{RhIr(cod)(CO)2(-O2napy)}2] (2A).

Table S5. Coordinates (xyz-coordinates) for the optimized geometry of complex [{RhIr(cod)(CO)2(-O2napy)}2]
(2A)

---------------------------------------------------------
Center Coordinates (Angstroms)
Number Element X Y Z
---------------------------------------------------------
1 Ir 0.006708 4.418170 0.058928
2 Rh -0.090786 1.432639 -0.646552
3 Rh 0.090786 -1.432639 -0.646552
4 Ir -0.006708 -4.418170 0.058928
5 O -0.879775 3.283413 1.641496
6 O -1.904493 -3.493391 0.323163
7 O 1.904493 3.493391 0.323163
8 O 0.879775 -3.283413 1.641496
9 N -1.310026 1.077350 1.085248
10 N -1.600996 -1.236481 0.695435
11 N 1.600996 1.236481 0.695435
12 N 1.310026 -1.077350 1.085248
13 C -1.490561 2.185830 1.868322
14 C -2.388127 2.134188 2.989809
15 H -2.502408 3.039078 3.573332
16 C -3.072920 0.989609 3.256427
17 H -3.780872 0.942161 4.079939
18 C -2.860377 -0.172720 2.471663
19 C -1.918869 -0.109338 1.406499
20 C -3.528290 -1.396494 2.713384
21 H -4.265051 -1.441498 3.511398
22 C -3.240168 -2.499113 1.964623
23 H -3.716216 -3.459073 2.119112
24 C -2.216163 -2.424137 0.969544
25 C 2.216163 2.424137 0.969544
26 C 3.240168 2.499113 1.964623
27 H 3.716216 3.459073 2.119112
28 C 3.528290 1.396494 2.713384
 S22

29 H 4.265051 1.441498 3.511398

30 C 2.860377 0.172720 2.471663
31 C 1.918869 0.109338 1.406499
32 C 3.072920 -0.989609 3.256427
33 H 3.780872 -0.942161 4.079939
34 C 2.388127 -2.134188 2.989809
35 H 2.502408 -3.039078 3.573332
36 C 1.490561 -2.185830 1.868322
37 C 0.679932 5.205207 -1.782219
38 H 1.499322 4.594057 -2.158359
39 C 1.008592 6.119223 -0.736986
40 H 2.036158 6.090971 -0.376623
41 C 0.266818 7.437096 -0.510860
42 H -0.117412 7.812745 -1.465209
43 H 0.973231 8.193040 -0.152668
44 C -0.879775 7.273637 0.510148
45 H -1.669975 8.019373 0.335318
46 H -0.493196 7.465718 1.517214
47 C -1.455559 5.866946 0.510645
48 H -1.928214 5.581374 1.450106
49 C -1.868645 5.138609 -0.648264
50 H -2.642174 4.387724 -0.491188
51 C -1.806578 5.712209 -2.067018
52 H -1.971654 6.794745 -2.032927
53 H -2.631737 5.302922 -2.658529
54 C -0.464975 5.390892 -2.766401
55 H -0.216973 6.163554 -3.509238
56 H -0.569091 4.455963 -3.328282
57 C 1.455559 -5.866946 0.510645
58 H 1.928214 -5.581374 1.450106
59 C 1.868645 -5.138609 -0.648264
60 H 2.642174 -4.387724 -0.491188
61 C 1.806578 -5.712209 -2.067018
62 H 1.971654 -6.794745 -2.032927
63 H 2.631737 -5.302922 -2.658529
64 C 0.464975 -5.390892 -2.766401
65 H 0.216973 -6.163554 -3.509238
66 H 0.569091 -4.455963 -3.328282
67 C -0.679932 -5.205207 -1.782219
68 H -1.499322 -4.594057 -2.158359
69 C -1.008592 -6.119223 -0.736986
70 H -2.036158 -6.090971 -0.376623
71 C -0.266818 -7.437096 -0.510860
72 H 0.117412 -7.812745 -1.465209
73 H -0.973231 -8.193040 -0.152668
74 C 0.879775 -7.273637 0.510148
75 H 1.669975 -8.019373 0.335318
76 H 0.493196 -7.465718 1.517214
77 C 1.056204 1.746801 -2.112133
78 O 1.777223 1.911511 -2.991364
79 C 1.637619 -1.707657 -1.680693
80 O 2.602565 -1.885161 -2.280757
81 C -1.637619 1.707657 -1.680693
82 O -2.602565 1.885161 -2.280757
83 C -1.056204 -1.746801 -2.112133
84 O -1.777223 -1.911511 -2.991364
---------------------------------------------------------
 S23

Figure S17. Optimized geometry of complex [{RhIr(cod)(CO)2(-O2napy)}2] (2B).

Table S6. Coordinates (xyz-coordinates) for the optimized geometry of complex [{RhIr(cod)(CO)2(-O2napy)}2]
(2B)

--------------------------------------------------------
Center Atomic Coordinates (Angstroms)
Number Number X Y Z
--------------------------------------------------------
1 Ir -4.048738 -0.209344 0.088944
2 Rh -1.422495 -0.479041 -0.078157
3 Rh 1.347959 -0.443929 -0.073771
4 Ir 4.341849 -0.067755 0.154651
5 O -3.517698 1.414145 1.268511
6 O 3.376207 0.465142 1.943558
7 O -3.356856 1.148299 -1.751252
8 O 3.555808 1.583418 -0.873611
9 N -1.227141 1.070673 1.437772
10 N 1.114631 0.815023 1.638841
11 N -1.046577 1.203996 -1.544394
12 N 1.282806 1.347688 -1.252092
13 C -2.372951 1.721712 1.773424
14 C -2.368694 2.789879 2.729375
15 H -3.314236 3.274083 2.937384
16 C -1.207096 3.127166 3.350645
17 H -1.181080 3.913169 4.100674
18 C -0.005410 2.450764 3.025211
19 C -0.044027 1.439444 2.024243
20 C 1.228109 2.739410 3.656383
21 H 1.253585 3.505470 4.426994
22 C 2.358480 2.064809 3.304329
23 H 3.322544 2.244215 3.762943
24 C 2.296586 1.092951 2.257677
 S24

25 C -2.237284 1.681072 -2.037316

26 C -2.224719 2.825254 -2.919004
27 H -3.176347 3.148555 -3.323092
28 C -1.058024 3.474009 -3.179117
29 H -1.039845 4.355819 -3.815304
30 C 0.161033 3.018174 -2.610524
31 C 0.120210 1.845956 -1.803031
32 C 1.398376 3.677190 -2.789034
33 H 1.430670 4.576290 -3.399742
34 C 2.530995 3.198252 -2.197172
35 H 3.497141 3.676309 -2.297927
36 C 2.466033 2.003069 -1.411549
37 C -4.818269 -2.201387 -0.576274
38 H -3.974854 -2.880844 -0.654226
39 C -4.944850 -1.253279 -1.608479
40 H -4.190826 -1.271335 -2.391105
41 C -6.218654 -0.520192 -1.993165
42 H -6.838003 -1.161278 -2.638577
43 H -5.911429 0.335952 -2.601107
44 C -7.017618 -0.007316 -0.776297
45 H -7.730542 -0.761728 -0.427783
46 H -7.619675 0.853739 -1.083533
47 C -6.086772 0.411535 0.360875
48 H -6.066839 1.478015 0.579372
49 C -5.686336 -0.453724 1.436366
50 H -5.432041 0.038657 2.374030
51 C -6.121481 -1.899005 1.596513
52 H -7.155642 -1.953726 1.967152
53 H -5.488182 -2.346975 2.367677
54 C -5.968989 -2.706845 0.291627
55 H -6.894808 -2.686238 -0.291193
56 H -5.786836 -3.758712 0.532881
57 C 5.933064 0.021708 -1.235060
58 H 5.853906 0.971544 -1.763024
59 C 5.030292 -1.002683 -1.643643
60 C 4.362268 -0.747960 -2.464579
61 C 5.319945 -2.497059 -1.484073
62 H 6.397715 -2.672605 -1.568336
63 H 4.862227 -3.043111 -2.314969
64 C 4.783273 -3.055853 -0.145751
65 H 5.379174 -3.920042 0.182795
66 H 3.765816 -3.433285 -0.296114
67 C 4.722723 -2.002806 0.948794
68 H 3.993561 -2.208790 1.731252
69 C 5.793854 -1.138028 1.305204
70 H 5.770183 -0.728017 2.313983
71 C 7.170580 -1.184240 0.642086
72 H 7.387660 -2.206280 0.314383
73 H 7.936511 -0.937435 1.384249
74 C 7.269404 -0.200939 -0.546144
75 H 8.026611 -0.538683 -1.269400
76 H 7.610437 0.772891 -0.177661
77 C -1.557667 -1.796485 -1.366269
78 O -1.621051 -2.606889 -2.187614
79 C 1.583749 -1.440762 -1.658621
80 O 1.765845 -2.008539 -2.639333
81 C -2.688193 -1.443120 1.175830
82 O -2.771984 -2.213598 2.060200
83 C 1.203596 -1.978239 1.033413
84 O 1.120998 -2.892159 1.721056
--------------------------------------------------------
 S25

Figure S18. Optimized geometry of the peroxoacyl complex B.

Table S7. Coordinates (xyz-coordinates) for the optimized geometry of the peroxoacyl complex B

---------------------------------------------------------
Center Coordinates (Angstroms)
Number Element X Y Z
---------------------------------------------------------
1 Ir -3.914194 -0.078942 -0.043821
2 Rh -1.378105 -0.420139 -0.432962
3 Rh 1.399452 -0.323958 -0.448668
4 Ir 4.391539 -0.040996 0.135937
5 O -3.245226 0.638877 1.794399
6 O 3.448728 -1.245457 1.590490
7 O -3.490169 1.900955 -0.747902
8 O 3.320863 1.680609 0.747691
9 N -1.095670 -0.204302 1.705845
10 N 1.200270 -0.731867 1.644537
11 N -1.183006 1.813361 -0.447641
12 N 1.122554 1.750205 0.034962
13 C -2.181196 0.220061 2.398595
14 C -2.178015 0.249914 3.829059
15 H -3.082641 0.576646 4.325978
16 C -1.068325 -0.162495 4.503923
17 H -1.051907 -0.186393 5.590334
18 C 0.094910 -0.547525 3.792772
19 C 0.060232 -0.504156 2.371344
20 C 1.297919 -0.941170 4.427585
21 H 1.321482 -1.004328 5.512402
22 C 2.409448 -1.217843 3.687596
23 H 3.354485 -1.508947 4.128270
24 C 2.366018 -1.056088 2.267302
25 C -2.355927 2.492861 -0.547748
26 C -2.383573 3.922642 -0.450435
27 H -3.335982 4.418419 -0.590538
28 C -1.242811 4.592105 -0.121859
29 H -1.247068 5.671582 0.006064
 S26

30 C -0.035305 3.883493 0.090360

31 C -0.037644 2.475161 -0.116939
32 C 1.159225 4.504905 0.531201
33 H 1.161932 5.579430 0.696159
34 C 2.275623 3.760599 0.762483
35 H 3.204607 4.185875 1.120957
36 C 2.255057 2.348301 0.506708
37 C -4.954482 -1.394081 -1.495069
38 H -4.225648 -2.163632 -1.728453
39 C -4.770092 -0.141565 -2.098337
40 H -3.942372 -0.041283 -2.791400
41 C -5.817532 0.942121 -2.254501
42 H -6.427973 0.730988 -3.144711
43 H -5.283905 1.874422 -2.451185
44 C -6.720634 1.134993 -1.016314
45 H -7.586523 0.468289 -1.064087
46 H -7.120565 2.153752 -1.027476
47 C -5.986432 0.914693 0.295831
48 H -5.684488 1.805337 0.839394
49 C -5.958793 -0.294095 0.983846
50 H -5.666884 -0.263138 2.030477
51 C -6.566915 -1.597660 0.514057
52 H -7.649224 -1.595407 0.707762
53 H -6.131985 -2.389524 1.125427
54 C -6.294160 -1.915028 -0.974227
55 H -7.095447 -1.521559 -1.608061
56 H -6.310238 -3.000660 -1.105976
57 C 5.848155 1.307771 -0.588661
58 H 5.605617 2.296868 -0.201223
59 C 5.060238 0.850191 -1.686432
60 H 4.303951 1.543018 -2.053492
61 C 5.558486 -0.165943 -2.717406
62 H 5.112460 0.060404 -3.691057
63 H 6.639756 -0.051889 -2.850306
64 C 5.211772 -1.619758 -2.319653
65 H 4.248328 -1.895051 -2.762337
66 H 5.946458 -2.323616 -2.737539
67 C 5.092117 -1.805716 -0.815743
68 H 4.465345 -2.642553 -0.514497
69 C 6.058829 -1.374875 0.135422
70 H 6.056820 -1.891560 1.094430
71 C 7.376705 -0.702256 -0.249161
72 H 7.701842 -1.064620 -1.230029
73 H 8.156033 -1.005612 0.457263
74 C 7.253750 0.837473 -0.252853
75 H 7.988500 1.286296 -0.937873
76 H 7.492972 1.218687 0.746152
77 C -1.573633 -0.652281 -2.264680
78 O -1.624576 -0.800232 -3.407615
79 C 1.564377 0.153048 -2.264679
80 O 1.696821 0.485170 -3.356030
81 C -1.699417 -2.403962 -0.229590
82 O -0.931859 -3.271608 -0.589934
83 C 1.687386 -2.176524 -0.822057
84 O 1.973430 -3.257808 -1.058172
85 O -3.711131 -1.846558 0.935326
86 O -2.908776 -2.845988 0.248644
---------------------------------------------------------
 S27

Figure S19. Optimized geometry of the oxide bridging complex C.

Table S8. Coordinates (xyz-coordinates) for the optimized geometry of the oxide bridging complex C.

---------------------------------------------------------
Center Coordinates (Angstroms)
Number Element X Y Z
---------------------------------------------------------
1 Ir 3.976869 -0.194584 -0.180130
2 Rh 1.453807 -0.465095 -0.141397
3 Rh -1.296000 -0.445426 -0.138853
4 Ir -4.272072 0.005424 -0.140487
5 O 3.480010 1.792453 -0.610594
6 O -3.379388 1.112254 -1.679040
7 O 3.500074 0.361880 1.985886
8 O -3.420553 1.215491 1.348134
9 N 1.209842 1.530470 -0.963443
10 N -1.116918 1.343735 -1.278536
11 N 1.168103 0.488265 1.824357
12 N -1.160864 0.787750 1.615050
13 C 2.365163 2.234290 -1.076401
14 C 2.383672 3.528134 -1.695391
15 H 3.335083 4.042355 -1.747634
16 C 1.231873 4.045621 -2.202182
17 H 1.222155 5.015001 -2.693643
18 C 0.019066 3.319025 -2.096660
19 C 0.046072 2.055743 -1.440839
20 C -1.210041 3.789909 -2.614648
21 H -1.229796 4.751034 -3.121996
22 C -2.347769 3.049494 -2.479220
23 H -3.309308 3.366994 -2.862080
24 C -2.294273 1.803528 -1.781820
25 C 2.372675 0.773607 2.431494
26 C 2.385752 1.555045 3.641062
27 H 3.348758 1.723014 4.107183
28 C 1.230018 2.080982 4.128730
29 H 1.231309 2.695604 5.025541
 S28

30 C 0.001211 1.856438 3.457113

31 C 0.012613 1.034672 2.295251
32 C -1.221382 2.436218 3.869898
33 H -1.229422 3.065706 4.756295
34 C -2.364291 2.220070 3.159272
35 H -3.318856 2.653914 3.428959
36 C -2.326247 1.379429 1.999979
37 C 4.679730 -2.269680 -0.461833
38 H 3.782918 -2.805572 -0.752476
39 C 4.818841 -1.918974 0.891905
40 H 4.046867 -2.255288 1.578321
41 C 6.110559 -1.492328 1.567502
42 H 6.702385 -2.379861 1.836951
43 H 5.828135 -1.006828 2.506248
44 C 6.942901 -0.500437 0.723323
45 H 7.648793 -1.033208 0.077924
46 H 7.554379 0.109040 1.396154
47 C 6.053182 0.420244 -0.111386
48 H 6.059874 1.469217 0.179128
49 C 5.656748 0.151700 -1.462815
50 H 5.407250 1.020547 -2.068659
51 C 6.023409 -1.082782 -2.263455
52 H 7.051544 -1.006689 -2.647239
53 H 5.361027 -1.109487 -3.133550
54 C 5.836054 -2.378527 -1.451929
55 H 6.752992 -2.642062 -0.916818
56 H 5.631419 -3.210463 -2.132853
57 C -5.806866 -0.393826 1.262424
58 H -5.700408 0.321446 2.077487
59 C -4.897217 -1.489887 1.263335
60 H -4.194877 -1.523856 2.094362
61 C -5.202633 -2.843284 0.617481
62 H -6.277388 -3.044450 0.678751
63 H -4.716579 -3.635555 1.195382
64 C -4.721649 -2.911733 -0.850775
65 H -5.334650 -3.618494 -1.429068
66 H -3.701176 -3.309457 -0.876415
67 C -4.698323 -1.550638 -1.526551
68 H -4.000557 -1.473039 -2.359236
69 C -5.776481 -0.624149 -1.526491
70 H -5.788870 0.104650 -2.335763
71 C -7.125600 -0.900387 -0.862925
72 H -7.337148 -1.974348 -0.890858
73 H -7.918571 -0.422425 -1.446887
74 C -7.169980 -0.376196 0.590319
75 H -7.902334 -0.941461 1.185764
76 H -7.515908 0.663379 0.585622
77 C 1.575584 -2.200673 0.472787
78 O 1.587622 -3.287554 0.866813
79 C -1.496489 -1.961635 0.972932
80 O -1.664676 -2.850177 1.679010
81 C -1.174090 -1.456590 -1.741975
82 O -1.099246 -2.045899 -2.721935
83 O 2.742209 -0.725538 -1.688679
---------------------------------------------------------
 S29

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