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Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2001
New insight into the dynamic behaviour of manganese ketene complexes:
evidence for the scrambling of a carbene moiety over carbonyl ligands
Yannick Ortin, Yannick Coppel, Noël Lugan,* René Mathieu and Michael
J. McGlinchey‡
Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne,
31077 Toulouse Cedex 4, France. Fax: +33 5 61 55 30 03; Tel: +33 5 61
33 31 71; Email: [email protected]
SUPPORTING INFORMATION
General
The complexes MeCpMn(CO)3 and CpMn(CO)3 were obtained from Alfa and
Aldrich, respectively. 13Cenriched Cp(13CO)3Mn (>15 %) was prepared
by photolysis of Cp(CO)3Mn in Et2O under a 13CO atmosphere. The
complexes MeCp(CO)2MnC(Ph)CCPh (1a), Cp(CO)2MnC(Ph)CCPh (1b), and
Cp(CO)2Mn2C,CPh2CCO] (5) were prepared following literature
procedures (1a, 1b: Y. Ortin, Y. Coppel, N. Lugan, R. Mathieu and M.
J. McGlinchey, J. C. S., Chem. Commun., 2001, 1690; 5: W. A. Herrmann,
Angew. Chem., Int. Ed. Engl., 1974, 13, 335). Tetrahydrofuran and
diethyl ether used for the synthesis were distilled under nitrogen
from sodium benzophenone ketyl just before use. Other solvents were
purified following standard procedures, and stored under nitrogen. All
synthetic manipulations were carried out using standard Schlenk
techniques under an atmosphere of dry nitrogen. A liquid N2/isopropanol
slush bath was used to maintain samples at the desired low
temperature. Chromatographic separation of the complexes was performed
on alumina (neutral, activity III (Aldrich)). Solution IR spectra were
recorded on a PerkinElmer 983G spectrophotometer with 0.1 mm cells
equipped with CaF2 windows. 1H and 13C NMR spectra were obtained on
Bruker WM250, DPX300, or AMX400 spectrometers and were referenced to
the residual signals of the deuterated solvent. Mass spectra were
recorded on AEIMS9, or Nermag R1010 mass spectrometers (EI).
Microanalyses of C and H elements were performed on a PerkinElmer
2400 CHN analyser.
Synthesis of RCpMnCo2(CO)6[34CC(Ph)C(Ph)C(O)] (3; 3a: R Me; 3b:
R H)) and RCp(CO)2Mn[34OCC(Ph)CCPh]Co2(CO)6 (4; 4a: R Me;
4b: R H)
A solution of complex MeCp(CO)2MnC(Ph)CCPh (1a) (0.31 g, 0.8 mmol)
in hexane (20 mL) was transferred by means of a canula into a Schlenk
flask containing Co2(CO)8 (0,28 g, 0,8 mmol). After stirring for 5
min, the IR of the solution showed a pattern that suggested the
formation of MeCp(CO)2Mn[33C(Ph)CCPh]Co2(CO)6, [IR (hexane):2086,
2053, 2031, 1977, 1920 (CO) cm1]. After 3 hours, after which time IR
monitoring showed the reaction medium ceased evolving, stirring was
discontinued. The black microcrystalline solid of MeCpMnCo2(CO)6[34CC(Ph)C(Ph)C(O)]
(3a) that had formed was separated from the solution by filtration,
washed with hexane (3 x 2 mL) and dried under vacuum (0.23 g, 0.36
mmol, 45% yield). The filtrate was evaporated to dryness and the
residue was separated by column chromatography on alumina. A first
elution with a 1:20 diethylether/pentane mixture of gave a
browngreenish band containing MeCp(CO)3Mn and traces of unidentified
Cocontaining complexes. A second elution with a 1:10
diethylether/pentane mixture gave a dark green band containing
MeCp(CO)2Mn[34OCC(Ph)CCPh]Co2(CO)6 (4a). Removal of the
solvents under high vacuum left complex 4a as a brown solid (0.100 g,
0.14 mmol, 18% yield).
Crystals of 3a and 4a suitable for the Xray diffraction studies were
grown from dichloromethene and diethyl ether/hexane solutions,
respectively, in the cold.
Complexes CpMnCo2(CO)6[34CC(Ph)C(Ph)C(O)] (3b) and Cp(CO)2Mn[34OCC(Ph)CCPh]Co2(CO)6
(4b), and CpMnCo2(13CO)6[34CC(Ph)C(Ph)C(O)] (4b13C) and Cp(13CO)2Mn[34O13CC(Ph)CCPh]Co2(CO)6
(4b13C) were synthesized as above from Cp(CO)2MnC(Ph)CCPh and Cp(13CO)2Mn13C(Ph)CCPh,
respectively, and Co2(CO)8.
3a: 1H NMR (300 MHz, dichloromethaneD2, 233 K): 7.567.20 (10H,
Ph), 5.11, 4.67, 4.56 (m, 4H, MeCp), 1.90 (s, 3H, MeCp); 13C{1H} NMR
(75.5 MHz, dichloromethaneD2, 233 K) : 329.3 (C), 237.8 (br;
(MnCO), 206.5, 203.5, 197.4, 195.4 (CoCO), 211.7 (CO), 147.2 (C(Ph)C(Ph)),
135.1, 132.3, 131.9, 130.6, 129.8, 128.8, 128.3, 128.2 (Ph), 105.8,
90.9, 90.7, 87.2, 87.0 (MeCp), 86.9 (C(Ph)C(Ph)), 12.5 (MeCp);
elemental analysis calcd (%) for C28H17Co2MnO7 : C 52.67, H 2.69;
found: C 51.70, H 2.76; IR (CH2Cl2): 2065(m), 2032(s), 2012(m),
1883(m) 1844(w), 1629(w) (CO) cm1.
3b: 1H NMR (300 MHz, dichloromethaneD2, 233 K): 7.557.24 (10H,
Ph), 4.90 (s, 5H, Cp); 13C{1H} NMR (20 MHz, dichloromethaneD2, 308 K)
: 329.2 C, 238.1, 237.1 (MnCO), 213.4 (CO), 206.6, 203.5,
197.2, 195.4 (CoCO), 211.7 (CO), 147.2 (C(Ph)C(Ph)), 134.6, 132.2,
130.6, 130.1, 129.0, 128.6 (Ph), 89.6 (Cp), 86.6 (C(Ph)C(Ph));
elemental analysis calcd (%) for C30H17Co2MnO9 : C 51.88, H 2.47;
found: C 51.20, H 2.68; IR (CH2Cl2): 2065(m), 2032(s), 2012(m),
1883(m) 1844(w), 1629(w) (CO) cm1.
4a: 1H NMR (400 MHz, dichloromethaneD2, 298 K): 7.477.19 (m,
10H, Ph), 4.23 (s, 4H, MeCp), 1.97 (s, 3H, MeCp); 13C{1H} NMR (100
MHz, dichloromethaneD2, 298 K): 200.0 (Co2(CO)6) 145.5, 139.9,
130.1, 129.0, 128.6, 127.5, 127.0 (Ph), 105.1, 89.6, 89.3 (MeCp),
107.2, 95.9 (CC), 13.3 (MeCp), 4.0 (OCC); 1H NMR (400 MHz,
tolueneD8, 193 K): 8.26.7 (m, Ph), 4.49, 4.32, 4.28 (minor
diastereomer), 4.19 (minor diastereomer), 4.02, 3.87 (m, MeCp), 1.94
(s, MeCp, minor diastereomer), 1.90 (s, MeCp, major diastereomer); 13C{1H}
NMR (100 MHz, tolueneD8, 193 K): 251.4 (OCC, major
diastereomer), 249.1 (OCC, minor diastereomer), 231.9, 227.2 (MnCO,
major diastereomer), 231.9, 224.1 (MnCO, minor diastereomer), 199.8
(CoCO, major diastereomer), 199.1 (CoCO, minor diastereomer),
145.4123.1 (Ph), 108.8, 91.7 (CC, minor diastereomer), 105.0, 97.7
(CC, major diastereomer), 106.4, 90.9, 90.1, 89.1, 88.8, 86.8, 84.6
(MeCp), 13.3 (MeCp), 4.0 (OCC); elemental analysis calcd (%) for C30H17Co2MnO9
: C 51.88, H 2.47; found: C 52.39, H 2.57; IR (CH2Cl2): 2087(m),
2051(s), 2027(s), 1995(m, sh), 1940 (m), 1741 (w, br) (CO) cm1.
4b: 1H NMR (400 MHz, dichloromethaneD2, 298 K): 7.57.2 (m, 10H,
Ph), 4.32 (s, 5H, Cp); 13C{1H} NMR (100 MHz, dichloromethaneD2, 298
K): 199.5 (CoCO), 145.0, 140.0, 130.0, 129.1, 128.6, 127.5, 127.1
(Ph), 106.6, 89.2 (Cp), 106.6, 95.5 (CC), 3.9 (OCC); 1H NMR (400
MHz, tolueneD8, 193 K): 8.26.7 (m, 10H, Ph), 4.3 (br, Cp); 13C{1H}
NMR (100 MHz, tolueneD8, 193 K): 250.2 (OCC, major
diastereomer), 248.5 (OCC, minor diastereomer), 231.5, 226.9 (MnCO,
major diastereomer), 231.5, 223.8 (MnCO, minor diastereomer), 199.7
(CoCO), 145.4123.1 (Ph), 108.2, 93.1 (CC, minor diastereomer),
104.5, 97.2 (CC, major diastereomer), 89.9 (major diastereomer)
88.7 (Cp, minor diastereomer), 3.7 (OCC).
Spectroscopic characterization of complex Cp(CO)2Mn2OCCPh2) (5)
5: 1H NMR (300 MHz, dichloromethaneD2, 298 K): 7.57.0 (10H, Ph),
4.52 (s, 5H, Cp); 13C{1H} NMR (20 MHz, dichloromethaneD2, 308 K):
237.6 br, MnCO/CCO), 143.2, 130.5, 130.0, 127.4 (Ph), 90.4
(Cp), 3.3 (Ph2CCO). 1H NMR (300 MHz, dichloromethaneD2, 193 K):
7.97.0 (10H, Ph), 4.5 (br s, 5H, Cp); 13C{1H} NMR (75.5 MHz,
dichloromethaneD2, 193 K): 254.5 (Ph2CCO), 231.5, 226.5 (MnCO),
142.7, 140.5, 129.9, 129.3, 128.7, 127.5, 125.6 (Ph), 4.4, (Ph2CCO).
A 13Cenriched sample of 5, Cp(13CO)2Mn2O13CPh2)(513C) was
prepared according to Herrmann’s procedure (W. A. Herrmann, Angew.
Chem., Int. Ed. Engl., 1974, 13, 335) from 13Cenriched Cp(13CO)3Mn
and OCCPh2.
Xray Diffraction Studies
Crystals of 3a and 4a suitable for Xray diffraction were obtained
through recrystallisation from pentane/Et2O mixture in the cold. Data
were collected on an EnrafNonius CAD4 diffractometer. All
calculations were performed on a PCcompatible computer using the
WinGX system (Farrugia, L. J. J. Appl. Crystallogr. 1999, 32,
837838). Full crystallographic data are given in Table S1 and in the
attached CIF files. The structure was solved by using the SIR92
program (SIR92: A program for crystal structure solution. Altomare,
A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl.
Crystallogr. 1993, 26, 343350), which revealed the position of all
the nonhydrogen atoms. The structure was refined by using the
SHELXS97 program ([Includes SHELXS97, SHELXL97, CIFTAB] Programs for
Crystal Structure Analysis (Release 972). Sheldrick, G.M., Institüt
für Anorganische Chemie der Universität, Tammanstrasse 4, D3400
Göttingen, Germany, 1998). Atomic scattering factors were taken from
the usual tabulations (Hahn, T. Ed., International Tables for
Crystallography, Volume A, Kluwer Academic Publishers, Dordrecht, The
Netherlands, 1995). Anomalous dispersion terms for Mn were included in
Fc. All nonhydrogen atoms were allowed to vibrate anisotropically.
All the hydrogen atoms were set in idealized positions (CH 0.96 Å;
U 1.2Ueq attached C) and held fixed during refinements. Distances
and angles for 3a are given in Tables S2 whereas final atomic
coordinates for nonhydrogen atoms, anisotropic temperature factors,
and atomic coordinates for hydrogen atoms are given in Table S3 to S5,
respectively. Distances and angles for 4a are given in Tables S6,
whereas final atomic coordinates for nonhydrogen atoms, anisotropic
temperature factors, and atomic coordinates for hydrogen atoms are
given in Table S7 to S9, respectively.
Table S1. Crystal data and structure refinement for complexes 3a and
4a.
Identification code 3a 4a
Empirical formula C28H17Co2MnO7 C30H17Co2MnO9
Formula weight 638.22 694.24
Temperature, K 160(2) 293(1)
Wavelength, Å 0.71073
Crystal system monoclinic triclinic
Space group P21/n (#14) P1 bar (#2)
a/Å 10.283(1) 9.464(1)
b/Å 18.334(3) 10.214(1)
c/Å 14.535(2) 14.691(2)
/° 81.41(1)
/° 109.42(2) 90.00(1)
/° 82.70(1)
Volume, Å3 2584(1) 1392.6(6)
Z 4 2
Density (calculated), Mg/m3 1.640 1.656
Absorption coefficient, mm1 1.795 1.679
F(000) 1280 696
range for data collection, ° 2.13 to 22.97 2.03 to 22.98
Index ranges 02sigma(I)] R1 0.0293 R1 0.0352,
wR2 0.0646 wR2 0.0885
R indices (all data) R1 0.1175 R1 0.0565
wR2 0.0809 wR2 0.0947
Largest diff. peak and hole, e.Å3 0.430 and 0.312 0.759 and 0.335
Table S2. Atomic coordinates (x 104) and equivalent isotropic
displacement parameters (Å2 x 103) for 3a. U(eq) is defined as one
third of the trace of the orthogonalized Uij tensor.
x y z U(eq)
Co(1) 7455(1) 1981(1) 8847(1) 34(1)
Co(2) 8289(1) 3175(1) 9563(1) 36(1)
Mn(1) 6017(1) 2651(1) 9781(1) 38(1)
O(1) 8345(4) 2761(2) 11626(3) 73(1)
O(2) 6216(4) 1072(2) 10132(3) 66(1)
O(3) 8735(6) 4632(2) 10440(3) 124(2)
O(4) 11023(4) 2553(2) 10533(3) 91(2)
O(5) 5882(4) 1198(2) 7097(3) 69(1)
O(6) 9594(4) 886(2) 9780(3) 78(1)
O(7) 9431(3) 2210(2) 7887(2) 50(1)
C(1) 7613(6) 2767(3) 10818(4) 49(1)
C(2) 6288(5) 1668(3) 9885(4) 45(1)
C(3) 8561(6) 4077(3) 10093(4) 58(2)
C(4) 9959(6) 2777(3) 10159(4) 55(2)
C(5) 6474(5) 1500(3) 7789(4) 41(1)
C(6) 8746(5) 1296(3) 9439(3) 44(1)
C(7) 8542(5) 2488(2) 8146(3) 36(1)
C(8) 8157(4) 3266(2) 8022(3) 32(1)
C(9) 6887(4) 3426(2) 8158(3) 32(1)
C(10) 6507(4) 2855(2) 8675(3) 31(1)
C(11) 6116(5) 4126(2) 7853(3) 32(1)
C(12) 6680(5) 4809(3) 8095(3) 40(1)
C(13) 5926(6) 5431(3) 7794(4) 51(1)
C(14) 4584(6) 5384(3) 7192(4) 58(2)
C(15) 3996(5) 4709(3) 6908(4) 54(2)
C(16) 4757(5) 4087(3) 7241(4) 43(1)
C(41) 3869(5) 2462(3) 9513(4) 53(2)
C(42) 4536(6) 2564(4) 10511(4) 63(2)
C(44) 4771(6) 3592(3) 9752(6) 75(2)
C(45) 4004(5) 3097(3) 9041(5) 61(2)
C(46) 3047(7) 1824(4) 9048(5) 99(2)
C(43) 5087(7) 3258(5) 10654(6) 86(2)
C(31) 8906(5) 3783(2) 7574(3) 36(1)
C(32) 8209(5) 4104(3) 6688(4) 47(1)
C(33) 8842(7) 4591(3) 6253(4) 57(2)
C(34) 10213(7) 4745(3) 6720(5) 66(2)
C(35) 10941(6) 4420(3) 7584(5) 63(2)
C(36) 10278(5) 3930(3) 8003(4) 52(1)
Table S3. Selected bond lengths [Å] and angles [°] for 3a.
Co(1)C(5) 1.769(5)
Co(1)C(6) 1.823(5)
Co(1)C(10) 1.849(4)
Co(1)C(7) 1.977(5)
Co(1)C(2) 2.292(5)
Co(1)Co(2) 2.4531(9)
Co(1)Mn(1) 2.6218(9)
Co(2)C(4) 1.801(6)
Co(2)C(3) 1.806(6)
Co(2)C(10) 1.949(4)
Co(2)C(9) 2.122(4)
Co(2)C(8) 2.205(4)
Co(2)C(1) 2.284(5)
Co(2)C(7) 2.500(5)
Co(2)Mn(1) 2.6418(9)
Mn(1)C(2) 1.821(5)
Mn(1)C(1) 1.835(6)
Mn(1)C(10) 1.876(4)
O(1)C(1) 1.164(6)
O(2)C(2) 1.161(5)
O(3)C(3) 1.123(6)
O(4)C(4) 1.125(6)
O(5)C(5) 1.132(5)
O(6)C(6) 1.133(5)
O(7)C(7) 1.212(5)
C(7)C(8) 1.475(6)
C(8)C(9) 1.415(6)
C(8)C(31) 1.499(6)
C(9)C(10) 1.416(6)
C(9)C(11) 1.497(6)
C(5)Co(1)C(6) 100.5(2)
C(5)Co(1)C(10) 101.1(2)
C(6)Co(1)C(10) 158.4(2)
C(5)Co(1)C(7) 92.5(2)
C(6)Co(1)C(7) 96.9(2)
C(10)Co(1)C(7) 83.44(19)
C(5)Co(1)C(2) 100.11(19)
C(6)Co(1)C(2) 88.60(19)
C(10)Co(1)C(2) 86.44(18)
C(7)Co(1)C(2) 165.16(18)
C(5)Co(1)Co(2) 146.32(16)
C(6)Co(1)Co(2) 108.50(16)
C(10)Co(1)Co(2) 51.56(13)
C(7)Co(1)Co(2) 67.73(13)
C(2)Co(1)Co(2) 97.46(13)
C(5)Co(1)Mn(1) 115.29(15)
C(6)Co(1)Mn(1) 121.74(14)
C(10)Co(1)Mn(1) 45.68(13)
C(7)Co(1)Mn(1) 124.02(14)
C(2)Co(1)Mn(1) 42.86(13)
Co(2)Co(1)Mn(1) 62.64(2)
C(4)Co(2)C(3) 100.3(2)
C(4)Co(2)C(10) 137.2(2)
C(3)Co(2)C(10) 122.4(2)
C(4)Co(2)C(9) 141.7(2)
C(3)Co(2)C(9) 99.9(2)
C(10)Co(2)C(9) 40.43(16)
C(4)Co(2)C(8) 104.3(2)
C(3)Co(2)C(8) 108.2(2)
C(10)Co(2)C(8) 67.85(17)
C(9)Co(2)C(8) 38.13(16)
C(4)Co(2)C(1) 88.7(2)
C(3)Co(2)C(1) 90.2(2)
C(10)Co(2)C(1) 87.79(19)
C(9)Co(2)C(1) 123.33(18)
C(8)Co(2)C(1) 154.70(18)
C(4)Co(2)Co(1) 89.18(17)
C(3)Co(2)Co(1) 168.67(19)
C(10)Co(2)Co(1) 48.00(12)
C(9)Co(2)Co(1) 75.80(11)
C(8)Co(2)Co(1) 75.03(11)
C(1)Co(2)Co(1) 83.70(13)
C(4)Co(2)C(7) 81.30(19)
C(3)Co(2)C(7) 140.3(2)
C(10)Co(2)C(7) 68.59(16)
C(9)Co(2)C(7) 62.60(16)
C(8)Co(2)C(7) 35.85(14)
C(1)Co(2)C(7) 129.47(16)
Co(1)Co(2)C(7) 47.03(10)
C(4)Co(2)Mn(1) 122.34(18)
C(3)Co(2)Mn(1) 107.42(19)
C(10)Co(2)Mn(1) 45.18(12)
C(9)Co(2)Mn(1) 81.29(12)
C(8)Co(2)Mn(1) 113.02(11)
C(1)Co(2)Mn(1) 42.99(14)
Co(1)Co(2)Mn(1) 61.81(2)
C(7)Co(2)Mn(1) 104.70(11)
C(2)Mn(1)C(1) 88.6(2)
C(2)Mn(1)C(10) 101.0(2)
C(1)Mn(1)C(10) 105.0(2)
C(2)Mn(1)Co(1) 58.87(15)
C(1)Mn(1)Co(1) 88.58(16)
C(10)Mn(1)Co(1) 44.84(13)
C(2)Mn(1)Co(2) 104.65(16)
C(1)Mn(1)Co(2) 58.05(16)
C(10)Mn(1)Co(2) 47.46(13)
Co(1)Mn(1)Co(2) 55.55(2)
O(1)C(1)Mn(1) 158.2(5)
O(1)C(1)Co(2) 122.8(4)
Mn(1)C(1)Co(2) 79.0(2)
O(2)C(2)Mn(1) 159.1(4)
O(2)C(2)Co(1) 122.7(4)
Mn(1)C(2)Co(1) 78.27(18)
O(3)C(3)Co(2) 178.7(5)
O(4)C(4)Co(2) 177.5(5)
O(5)C(5)Co(1) 177.5(5)
O(6)C(6)Co(1) 176.2(4)
O(7)C(7)C(8) 124.7(4)
O(7)C(7)Co(1) 125.2(4)
C(8)C(7)Co(1) 110.1(3)
O(7)C(7)Co(2) 139.8(3)
C(8)C(7)Co(2) 61.1(2)
Co(1)C(7)Co(2) 65.23(13)
C(9)C(8)C(7) 113.9(4)
C(9)C(8)C(31) 124.2(4)
C(7)C(8)C(31) 120.6(4)
C(9)C(8)Co(2) 67.7(2)
C(7)C(8)Co(2) 83.0(3)
C(31)C(8)Co(2) 128.4(3)
C(8)C(9)C(10) 110.6(4)
C(8)C(9)C(11) 123.9(4)
C(10)C(9)C(11) 125.4(4)
C(8)C(9)Co(2) 74.1(2)
C(10)C(9)Co(2) 63.2(2)
C(11)C(9)Co(2) 126.5(3)
C(9)C(10)Co(1) 119.1(3)
C(9)C(10)Mn(1) 143.3(3)
Co(1)C(10)Mn(1) 89.48(18)
C(9)C(10)Co(2) 76.4(3)
Co(1)C(10)Co(2) 80.44(17)
Mn(1)C(10)Co(2) 87.36(17)
Table S4. Anisotropic displacement parameters (Å2 x 103) for 3a. The
anisotropic
displacement factor exponent takes the form: 22[ h2a*2U11 + ... + 2
h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
Co(1) 41(1) 30(1) 34(1) 0(1) 15(1) 2(1)
Co(2) 38(1) 34(1) 35(1) 4(1) 12(1) 1(1)
Mn(1) 43(1) 37(1) 40(1) 1(1) 23(1) 1(1)
O(1) 74(3) 101(3) 36(2) 2(2) 9(2) 18(3)
O(2) 95(3) 45(2) 81(3) 15(2) 60(3) 0(2)
O(3) 209(6) 44(3) 70(3) 22(2) 16(3) 3(3)
O(4) 51(3) 112(4) 87(3) 9(3) 6(3) 29(3)
O(5) 72(3) 62(3) 57(3) 13(2) 1(2) 4(2)
O(6) 91(3) 79(3) 65(3) 21(2) 27(2) 47(3)
O(7) 57(2) 36(2) 69(2) 0(2) 39(2) 7(2)
C(1) 62(4) 43(3) 49(3) 4(3) 28(3) 2(3)
C(2) 52(3) 50(4) 42(3) 4(3) 26(3) 1(3)
C(3) 73(4) 49(4) 40(3) 1(3) 2(3) 1(3)
C(4) 54(4) 61(4) 46(3) 11(3) 14(3) 1(3)
C(5) 46(3) 35(3) 44(3) 3(3) 20(3) 4(3)
C(6) 53(4) 45(3) 39(3) 3(3) 23(3) 6(3)
C(7) 34(3) 35(3) 37(3) 7(2) 10(2) 3(2)
C(8) 32(3) 32(3) 31(3) 1(2) 10(2) 2(2)
C(9) 31(3) 29(3) 32(3) 2(2) 7(2) 2(2)
C(10) 32(3) 29(3) 32(3) 1(2) 11(2) 4(2)
C(11) 37(3) 32(3) 32(3) 5(2) 17(2) 5(2)
C(12) 37(3) 39(3) 47(3) 3(3) 19(3) 4(3)
C(13) 68(4) 28(3) 67(4) 4(3) 38(4) 3(3)
C(14) 62(4) 49(4) 73(4) 17(3) 37(4) 21(3)
C(15) 42(3) 72(4) 47(4) 15(3) 14(3) 15(3)
C(16) 43(3) 40(3) 46(3) 2(3) 16(3) 2(3)
C(41) 46(3) 56(4) 65(4) 5(3) 28(3) 5(3)
C(42) 49(4) 100(5) 54(4) 14(4) 35(3) 10(4)
C(44) 68(5) 57(4) 122(6) 10(4) 59(5) 16(4)
C(45) 44(4) 72(4) 78(4) 18(4) 36(3) 18(3)
C(46) 75(5) 107(6) 118(6) 13(5) 34(4) 0(5)
C(43) 61(4) 126(7) 84(6) 55(5) 42(4) 4(5)
C(31) 49(3) 28(3) 39(3) 1(2) 26(3) 0(2)
C(32) 58(4) 40(3) 49(3) 1(3) 28(3) 4(3)
C(33) 80(5) 42(3) 65(4) 13(3) 44(4) 8(3)
C(34) 95(5) 45(4) 87(5) 5(4) 67(4) 4(4)
C(35) 57(4) 66(4) 78(5) 5(4) 38(4) 22(3)
C(36) 44(3) 58(4) 58(4) 5(3) 23(3) 5(3)
Table S5. Hydrogen coordinates (x 104) and isotropic displacement
parameters (Å2 x 103)
for 4a.
x y z U(eq)
H(12) 7604 4848 8476 48
H(13) 6322 5884 7998 61
H(14) 4072 5806 6975 69
H(15) 3089 4674 6493 65
H(16) 4352 3633 7053 51
H(42) 4598 2222 10996 76
H(44) 5023 4061 9637 90
H(45) 3650 3181 8372 73
H(46A) 3153 1740 8425 149
H(46B) 3357 1404 9455 149
H(46C) 2093 1913 8960 149
H(43) 5583 3465 11252 103
H(32) 7286 3988 6376 56
H(33) 8358 4809 5661 69
H(34) 10654 5079 6442 80
H(35) 11870 4527 7888 76
H(36) 10774 3698 8582 63
Table S6. Atomic coordinates (x 104) and equivalent isotropic
displacement parameters (Å2 x 103) for complex 4a. U(eq) is defined as
one third of the trace of the orthogonalized Uij tensor.
x y z U(eq)
Co(1) 4197(1) 3762(1) 2981(1) 35(1)
Co(2) 1882(1) 4564(1) 3351(1) 36(1)
Mn(1) 505(1) 690(1) 2856(1) 39(1)
O(1) 1455(4) 2672(4) 4292(3) 93(1)
O(2) 739(3) 2318(3) 1380(2) 65(1)
O(3) 1873(3) 890(3) 4202(2) 57(1)
O(4) 5951(3) 2024(3) 1839(3) 74(1)
O(5) 5967(4) 6300(3) 2809(3) 82(1)
O(6) 4894(4) 3107(4) 4797(3) 92(1)
O(7) 1032(3) 4864(4) 2826(2) 74(1)
O(8) 1602(4) 3941(4) 5246(2) 86(1)
O(9) 2977(4) 7423(3) 3684(2) 71(1)
C(1) 1034(5) 1929(4) 3714(3) 56(1)
C(2) 658(4) 1700(4) 1966(3) 47(1)
C(3) 1354(4) 1033(4) 3491(3) 38(1)
C(4) 5256(4) 2670(4) 2284(3) 48(1)
C(5) 5304(4) 5330(4) 2897(3) 47(1)
C(6) 4619(4) 3347(4) 4097(3) 52(1)
C(7) 88(5) 4740(4) 3049(3) 48(1)
C(8) 1689(5) 4181(4) 4523(3) 53(1)
C(9) 2561(4) 6321(4) 3559(3) 45(1)
C(10) 1736(3) 1444(3) 2624(2) 31(1)
C(11) 2216(3) 2857(3) 2639(2) 31(1)
C(12) 2586(4) 3849(3) 2142(2) 33(1)
C(21) 2338(4) 632(4) 3230(3) 50(1)
C(22) 1067(5) 1026(4) 3526(3) 56(1)
C(23) 250(5) 1372(4) 2748(4) 62(1)
C(24) 971(5) 1174(4) 1978(4) 65(1)
C(25) 2271(5) 716(4) 2271(3) 57(1)
C(26) 3542(5) 271(5) 3840(4) 75(2)
C(31) 2414(4) 490(3) 1933(2) 35(1)
C(32) 3218(4) 416(4) 2218(3) 45(1)
C(33) 3864(5) 1282(4) 1580(4) 63(1)
C(34) 3736(6) 1235(5) 662(4) 74(2)
C(35) 2948(5) 337(5) 369(3) 70(1)
C(36) 2279(4) 521(4) 992(3) 51(1)
C(41) 2572(4) 4251(3) 1221(2) 36(1)
C(42) 1818(5) 5238(5) 1035(3) 58(1)
C(43) 1792(5) 5578(5) 157(4) 72(1)
C(44) 2520(6) 4948(6) 538(3) 71(1)
C(45) 3282(7) 3986(6) 358(3) 89(2)
C(46) 3319(6) 3640(5) 514(3) 69(1)
Table S7. Selected Bond lengths [Å] and angles [°] for 4a.
Co(1)C(4) 1.801(5)
Co(1)C(6) 1.810(5)
Co(1)C(5) 1.819(4)
Co(1)C(12) 1.980(3)
Co(1)C(11) 2.011(3)
Co(1)Co(2) 2.4678(7)
Co(2)C(7) 1.792(5)
Co(2)C(9) 1.808(4)
Co(2)C(8) 1.826(5)
Co(2)C(11) 1.957(3)
Co(2)C(12) 1.967(3)
Mn(1)C(1) 1.769(5)
Mn(1)C(2) 1.799(5)
Mn(1)C(3) 1.958(4)
Mn(1)C(10) 2.207(3)
O(1)C(1) 1.157(5)
O(2)C(2) 1.148(5)
O(3)C(3) 1.192(4)
O(4)C(4) 1.129(5)
O(5)C(5) 1.128(5)
O(6)C(6) 1.131(5)
O(7)C(7) 1.137(5)
O(8)C(8) 1.125(5)
O(9)C(9) 1.132(5)
C(3)C(10) 1.431(5)
C(10)C(11) 1.454(5)
C(10)C(31) 1.502(5)
C(11)C(12) 1.346(5)
C(12)C(41) 1.473(5)
C(4)Co(1)C(6) 98.60(19)
C(4)Co(1)C(5) 97.75(18)
C(6)Co(1)C(5) 105.65(19)
C(4)Co(1)C(12) 102.68(16)
C(6)Co(1)C(12) 142.78(16)
C(5)Co(1)C(12) 101.33(17)
C(4)Co(1)C(11) 101.22(16)
C(6)Co(1)C(11) 106.62(16)
C(5)Co(1)C(11) 139.31(16)
C(12)Co(1)C(11) 39.41(14)
C(4)Co(1)Co(2) 150.43(13)
C(6)Co(1)Co(2) 98.48(13)
C(5)Co(1)Co(2) 100.63(13)
C(12)Co(1)Co(2) 51.05(10)
C(11)Co(1)Co(2) 50.56(10)
C(7)Co(2)C(9) 97.49(18)
C(7)Co(2)C(8) 101.96(19)
C(9)Co(2)C(8) 101.59(18)
C(7)Co(2)C(11) 104.11(16)
C(9)Co(2)C(11) 142.71(16)
C(8)Co(2)C(11) 103.16(16)
C(7)Co(2)C(12) 100.56(16)
C(9)Co(2)C(12) 106.48(16)
C(8)Co(2)C(12) 141.05(17)
C(11)Co(2)C(12) 40.13(14)
C(7)Co(2)Co(1) 151.62(13)
C(9)Co(2)Co(1) 96.13(13)
C(8)Co(2)Co(1) 99.51(14)
C(11)Co(2)Co(1) 52.53(10)
C(12)Co(2)Co(1) 51.54(10)
C(1)Mn(1)C(2) 92.3(2)
C(1)Mn(1)C(3) 86.10(18)
C(2)Mn(1)C(3) 113.64(16)
C(1)Mn(1)C(10) 103.16(16)
C(2)Mn(1)C(10) 77.33(14)
C(3)Mn(1)C(10) 39.63(14)
C(24)Mn(1)C(10) 106.78(15)
C(23)Mn(1)C(10) 97.36(15)
C(22)Mn(1)C(10) 121.75(15)
C(25)Mn(1)C(10) 142.93(16)
C(21)Mn(1)C(10) 159.33(15)
O(1)C(1)Mn(1) 175.1(4)
O(2)C(2)Mn(1) 178.0(4)
O(3)C(3)C(10) 141.1(4)
O(3)C(3)Mn(1) 139.2(3)
C(10)C(3)Mn(1) 79.6(2)
O(4)C(4)Co(1) 177.5(4)
O(5)C(5)Co(1) 177.1(4)
O(6)C(6)Co(1) 178.9(4)
O(7)C(7)Co(2) 177.5(4)
O(8)C(8)Co(2) 178.5(4)
O(9)C(9)Co(2) 179.4(4)
C(3)C(10)C(11) 116.4(3)
C(3)C(10)C(31) 117.8(3)
C(11)C(10)C(31) 116.5(3)
C(3)C(10)Mn(1) 60.77(19)
C(11)C(10)Mn(1) 122.1(2)
C(31)C(10)Mn(1) 111.7(2)
C(12)C(11)C(10) 146.7(3)
C(12)C(11)Co(2) 70.3(2)
C(10)C(11)Co(2) 138.2(2)
C(12)C(11)Co(1) 69.1(2)
C(10)C(11)Co(1) 125.3(2)
Co(2)C(11)Co(1) 76.90(12)
C(11)C(12)C(41) 145.4(3)
C(11)C(12)Co(2) 69.5(2)
C(41)C(12)Co(2) 134.3(3)
C(11)C(12)Co(1) 71.5(2)
C(41)C(12)Co(1) 130.6(2)
Co(2)C(12)Co(1) 77.41(13
Table S8. Anisotropic displacement parameters (Å2 x 103) for 4a. The
anisotropic
displacement factor exponent takes the form: 22[ h2a*2U11 + ... + 2
h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
Co(1) 31(1) 40(1) 34(1) 4(1) 2(1) 1(1)
Co(2) 39(1) 37(1) 31(1) 1(1) 4(1) 6(1)
Mn(1) 33(1) 39(1) 42(1) 7(1) 5(1) 2(1)
O(1) 94(3) 71(2) 101(3) 15(2) 58(2) 3(2)
O(2) 56(2) 74(2) 67(2) 30(2) 15(2) 1(2)
O(3) 63(2) 75(2) 34(2) 18(2) 8(1) 0(2)
O(4) 52(2) 77(2) 92(3) 3(2) 21(2) 20(2)
O(5) 74(2) 60(2) 105(3) 12(2) 14(2) 17(2)
O(6) 90(3) 135(3) 56(2) 34(2) 20(2) 16(2)
O(7) 50(2) 99(3) 75(2) 1(2) 3(2) 28(2)
O(8) 135(3) 87(3) 38(2) 14(2) 22(2) 20(2)
O(9) 87(2) 41(2) 84(2) 9(2) 8(2) 2(2)
C(1) 47(2) 54(3) 64(3) 8(2) 19(2) 7(2)
C(2) 28(2) 53(3) 56(3) 3(2) 6(2) 1(2)
C(3) 45(2) 35(2) 34(2) 3(2) 2(2) 4(2)
C(4) 34(2) 54(3) 54(3) 6(2) 4(2) 0(2)
C(5) 39(2) 46(3) 53(3) 4(2) 5(2) 1(2)
C(6) 41(2) 62(3) 53(3) 12(2) 5(2) 2(2)
C(7) 49(3) 51(2) 43(2) 2(2) 11(2) 10(2)
C(8) 68(3) 46(3) 43(3) 2(2) 8(2) 9(2)
C(9) 55(3) 43(3) 39(2) 4(2) 1(2) 11(2)
C(10) 29(2) 35(2) 28(2) 5(2) 0(2) 3(2)
C(11) 30(2) 36(2) 26(2) 2(2) 0(2) 5(2)
C(12) 31(2) 36(2) 30(2) 3(2) 2(2) 4(2)
C(21) 40(2) 48(2) 60(3) 16(2) 2(2) 11(2)
C(22) 54(3) 48(3) 65(3) 24(2) 2(2) 12(2)
C(23) 49(3) 33(2) 103(4) 14(2) 6(3) 1(2)
C(24) 65(3) 50(3) 68(3) 7(2) 17(3) 16(2)
C(25) 51(3) 54(3) 60(3) 11(2) 9(2) 17(2)
C(26) 58(3) 82(4) 81(4) 17(3) 13(3) 12(3)
C(31) 30(2) 36(2) 37(2) 3(2) 3(2) 4(2)
C(32) 42(2) 41(2) 52(2) 7(2) 4(2) 3(2)
C(33) 49(3) 43(3) 95(4) 5(3) 19(3) 10(2)
C(34) 78(4) 56(3) 80(4) 16(3) 32(3) 9(3)
C(35) 83(4) 79(4) 40(3) 14(2) 16(2) 3(3)
C(36) 53(3) 60(3) 37(2) 1(2) 5(2) 8(2)
C(41) 38(2) 36(2) 32(2) 8(2) 0(2) 4(2)
C(42) 65(3) 66(3) 49(3) 23(2) 4(2) 17(2)
C(43) 74(3) 82(4) 66(3) 39(3) 11(3) 8(3)
C(44) 81(3) 90(4) 45(3) 31(3) 6(3) 9(3)
C(45) 131(5) 107(5) 41(3) 28(3) 29(3) 38(4)
C(46) 94(4) 82(3) 43(3) 23(2) 20(3) 38(3)
Table S9. Hydrogen coordinates (x 104) and isotropic displacement
parameters (Å2 x 103)
for 4a.
x y z U(eq)
H(22) 809 1052 4133 67
H(23) 631 1683 2753 75
H(24) 661 1316 1375 77
H(25) 2966 506 1889 68
H(26A) 4037 357 3582 113
H(26B) 4189 1060 3888 113
H(26C) 3172 123 4441 113
H(32) 3327 446 2843 54
H(33) 4388 1900 1781 75
H(34) 4181 1809 237 89
H(35) 2862 304 258 84
H(36) 1738 1119 784 61
H(42) 1317 5685 1502 69
H(43) 1268 6249 41 86
H(44) 2493 5176 1127 85
H(45) 3790 3550 826 107
H(46) 3860 2980 625 83
‡ On sabbatical leave from: Department of Chemistry, McMaster
University, Hamilton, Ont., Canada L8S 4M1
This journal is © The Royal Society of Chemistry 2001
New insight into the dynamic behaviour of manganese ketene complexes:
evidence for the scrambling of a carbene moiety over carbonyl ligands
Yannick Ortin, Yannick Coppel, Noël Lugan,* René Mathieu and Michael
J. McGlinchey‡
Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne,
31077 Toulouse Cedex 4, France. Fax: +33 5 61 55 30 03; Tel: +33 5 61
33 31 71; Email: [email protected]
SUPPORTING INFORMATION
General
The complexes MeCpMn(CO)3 and CpMn(CO)3 were obtained from Alfa and
Aldrich, respectively. 13Cenriched Cp(13CO)3Mn (>15 %) was prepared
by photolysis of Cp(CO)3Mn in Et2O under a 13CO atmosphere. The
complexes MeCp(CO)2MnC(Ph)CCPh (1a), Cp(CO)2MnC(Ph)CCPh (1b), and
Cp(CO)2Mn2C,CPh2CCO] (5) were prepared following literature
procedures (1a, 1b: Y. Ortin, Y. Coppel, N. Lugan, R. Mathieu and M.
J. McGlinchey, J. C. S., Chem. Commun., 2001, 1690; 5: W. A. Herrmann,
Angew. Chem., Int. Ed. Engl., 1974, 13, 335). Tetrahydrofuran and
diethyl ether used for the synthesis were distilled under nitrogen
from sodium benzophenone ketyl just before use. Other solvents were
purified following standard procedures, and stored under nitrogen. All
synthetic manipulations were carried out using standard Schlenk
techniques under an atmosphere of dry nitrogen. A liquid N2/isopropanol
slush bath was used to maintain samples at the desired low
temperature. Chromatographic separation of the complexes was performed
on alumina (neutral, activity III (Aldrich)). Solution IR spectra were
recorded on a PerkinElmer 983G spectrophotometer with 0.1 mm cells
equipped with CaF2 windows. 1H and 13C NMR spectra were obtained on
Bruker WM250, DPX300, or AMX400 spectrometers and were referenced to
the residual signals of the deuterated solvent. Mass spectra were
recorded on AEIMS9, or Nermag R1010 mass spectrometers (EI).
Microanalyses of C and H elements were performed on a PerkinElmer
2400 CHN analyser.
Synthesis of RCpMnCo2(CO)6[34CC(Ph)C(Ph)C(O)] (3; 3a: R Me; 3b:
R H)) and RCp(CO)2Mn[34OCC(Ph)CCPh]Co2(CO)6 (4; 4a: R Me;
4b: R H)
A solution of complex MeCp(CO)2MnC(Ph)CCPh (1a) (0.31 g, 0.8 mmol)
in hexane (20 mL) was transferred by means of a canula into a Schlenk
flask containing Co2(CO)8 (0,28 g, 0,8 mmol). After stirring for 5
min, the IR of the solution showed a pattern that suggested the
formation of MeCp(CO)2Mn[33C(Ph)CCPh]Co2(CO)6, [IR (hexane):2086,
2053, 2031, 1977, 1920 (CO) cm1]. After 3 hours, after which time IR
monitoring showed the reaction medium ceased evolving, stirring was
discontinued. The black microcrystalline solid of MeCpMnCo2(CO)6[34CC(Ph)C(Ph)C(O)]
(3a) that had formed was separated from the solution by filtration,
washed with hexane (3 x 2 mL) and dried under vacuum (0.23 g, 0.36
mmol, 45% yield). The filtrate was evaporated to dryness and the
residue was separated by column chromatography on alumina. A first
elution with a 1:20 diethylether/pentane mixture of gave a
browngreenish band containing MeCp(CO)3Mn and traces of unidentified
Cocontaining complexes. A second elution with a 1:10
diethylether/pentane mixture gave a dark green band containing
MeCp(CO)2Mn[34OCC(Ph)CCPh]Co2(CO)6 (4a). Removal of the
solvents under high vacuum left complex 4a as a brown solid (0.100 g,
0.14 mmol, 18% yield).
Crystals of 3a and 4a suitable for the Xray diffraction studies were
grown from dichloromethene and diethyl ether/hexane solutions,
respectively, in the cold.
Complexes CpMnCo2(CO)6[34CC(Ph)C(Ph)C(O)] (3b) and Cp(CO)2Mn[34OCC(Ph)CCPh]Co2(CO)6
(4b), and CpMnCo2(13CO)6[34CC(Ph)C(Ph)C(O)] (4b13C) and Cp(13CO)2Mn[34O13CC(Ph)CCPh]Co2(CO)6
(4b13C) were synthesized as above from Cp(CO)2MnC(Ph)CCPh and Cp(13CO)2Mn13C(Ph)CCPh,
respectively, and Co2(CO)8.
3a: 1H NMR (300 MHz, dichloromethaneD2, 233 K): 7.567.20 (10H,
Ph), 5.11, 4.67, 4.56 (m, 4H, MeCp), 1.90 (s, 3H, MeCp); 13C{1H} NMR
(75.5 MHz, dichloromethaneD2, 233 K) : 329.3 (C), 237.8 (br;
(MnCO), 206.5, 203.5, 197.4, 195.4 (CoCO), 211.7 (CO), 147.2 (C(Ph)C(Ph)),
135.1, 132.3, 131.9, 130.6, 129.8, 128.8, 128.3, 128.2 (Ph), 105.8,
90.9, 90.7, 87.2, 87.0 (MeCp), 86.9 (C(Ph)C(Ph)), 12.5 (MeCp);
elemental analysis calcd (%) for C28H17Co2MnO7 : C 52.67, H 2.69;
found: C 51.70, H 2.76; IR (CH2Cl2): 2065(m), 2032(s), 2012(m),
1883(m) 1844(w), 1629(w) (CO) cm1.
3b: 1H NMR (300 MHz, dichloromethaneD2, 233 K): 7.557.24 (10H,
Ph), 4.90 (s, 5H, Cp); 13C{1H} NMR (20 MHz, dichloromethaneD2, 308 K)
: 329.2 C, 238.1, 237.1 (MnCO), 213.4 (CO), 206.6, 203.5,
197.2, 195.4 (CoCO), 211.7 (CO), 147.2 (C(Ph)C(Ph)), 134.6, 132.2,
130.6, 130.1, 129.0, 128.6 (Ph), 89.6 (Cp), 86.6 (C(Ph)C(Ph));
elemental analysis calcd (%) for C30H17Co2MnO9 : C 51.88, H 2.47;
found: C 51.20, H 2.68; IR (CH2Cl2): 2065(m), 2032(s), 2012(m),
1883(m) 1844(w), 1629(w) (CO) cm1.
4a: 1H NMR (400 MHz, dichloromethaneD2, 298 K): 7.477.19 (m,
10H, Ph), 4.23 (s, 4H, MeCp), 1.97 (s, 3H, MeCp); 13C{1H} NMR (100
MHz, dichloromethaneD2, 298 K): 200.0 (Co2(CO)6) 145.5, 139.9,
130.1, 129.0, 128.6, 127.5, 127.0 (Ph), 105.1, 89.6, 89.3 (MeCp),
107.2, 95.9 (CC), 13.3 (MeCp), 4.0 (OCC); 1H NMR (400 MHz,
tolueneD8, 193 K): 8.26.7 (m, Ph), 4.49, 4.32, 4.28 (minor
diastereomer), 4.19 (minor diastereomer), 4.02, 3.87 (m, MeCp), 1.94
(s, MeCp, minor diastereomer), 1.90 (s, MeCp, major diastereomer); 13C{1H}
NMR (100 MHz, tolueneD8, 193 K): 251.4 (OCC, major
diastereomer), 249.1 (OCC, minor diastereomer), 231.9, 227.2 (MnCO,
major diastereomer), 231.9, 224.1 (MnCO, minor diastereomer), 199.8
(CoCO, major diastereomer), 199.1 (CoCO, minor diastereomer),
145.4123.1 (Ph), 108.8, 91.7 (CC, minor diastereomer), 105.0, 97.7
(CC, major diastereomer), 106.4, 90.9, 90.1, 89.1, 88.8, 86.8, 84.6
(MeCp), 13.3 (MeCp), 4.0 (OCC); elemental analysis calcd (%) for C30H17Co2MnO9
: C 51.88, H 2.47; found: C 52.39, H 2.57; IR (CH2Cl2): 2087(m),
2051(s), 2027(s), 1995(m, sh), 1940 (m), 1741 (w, br) (CO) cm1.
4b: 1H NMR (400 MHz, dichloromethaneD2, 298 K): 7.57.2 (m, 10H,
Ph), 4.32 (s, 5H, Cp); 13C{1H} NMR (100 MHz, dichloromethaneD2, 298
K): 199.5 (CoCO), 145.0, 140.0, 130.0, 129.1, 128.6, 127.5, 127.1
(Ph), 106.6, 89.2 (Cp), 106.6, 95.5 (CC), 3.9 (OCC); 1H NMR (400
MHz, tolueneD8, 193 K): 8.26.7 (m, 10H, Ph), 4.3 (br, Cp); 13C{1H}
NMR (100 MHz, tolueneD8, 193 K): 250.2 (OCC, major
diastereomer), 248.5 (OCC, minor diastereomer), 231.5, 226.9 (MnCO,
major diastereomer), 231.5, 223.8 (MnCO, minor diastereomer), 199.7
(CoCO), 145.4123.1 (Ph), 108.2, 93.1 (CC, minor diastereomer),
104.5, 97.2 (CC, major diastereomer), 89.9 (major diastereomer)
88.7 (Cp, minor diastereomer), 3.7 (OCC).
Spectroscopic characterization of complex Cp(CO)2Mn2OCCPh2) (5)
5: 1H NMR (300 MHz, dichloromethaneD2, 298 K): 7.57.0 (10H, Ph),
4.52 (s, 5H, Cp); 13C{1H} NMR (20 MHz, dichloromethaneD2, 308 K):
237.6 br, MnCO/CCO), 143.2, 130.5, 130.0, 127.4 (Ph), 90.4
(Cp), 3.3 (Ph2CCO). 1H NMR (300 MHz, dichloromethaneD2, 193 K):
7.97.0 (10H, Ph), 4.5 (br s, 5H, Cp); 13C{1H} NMR (75.5 MHz,
dichloromethaneD2, 193 K): 254.5 (Ph2CCO), 231.5, 226.5 (MnCO),
142.7, 140.5, 129.9, 129.3, 128.7, 127.5, 125.6 (Ph), 4.4, (Ph2CCO).
A 13Cenriched sample of 5, Cp(13CO)2Mn2O13CPh2)(513C) was
prepared according to Herrmann’s procedure (W. A. Herrmann, Angew.
Chem., Int. Ed. Engl., 1974, 13, 335) from 13Cenriched Cp(13CO)3Mn
and OCCPh2.
Xray Diffraction Studies
Crystals of 3a and 4a suitable for Xray diffraction were obtained
through recrystallisation from pentane/Et2O mixture in the cold. Data
were collected on an EnrafNonius CAD4 diffractometer. All
calculations were performed on a PCcompatible computer using the
WinGX system (Farrugia, L. J. J. Appl. Crystallogr. 1999, 32,
837838). Full crystallographic data are given in Table S1 and in the
attached CIF files. The structure was solved by using the SIR92
program (SIR92: A program for crystal structure solution. Altomare,
A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl.
Crystallogr. 1993, 26, 343350), which revealed the position of all
the nonhydrogen atoms. The structure was refined by using the
SHELXS97 program ([Includes SHELXS97, SHELXL97, CIFTAB] Programs for
Crystal Structure Analysis (Release 972). Sheldrick, G.M., Institüt
für Anorganische Chemie der Universität, Tammanstrasse 4, D3400
Göttingen, Germany, 1998). Atomic scattering factors were taken from
the usual tabulations (Hahn, T. Ed., International Tables for
Crystallography, Volume A, Kluwer Academic Publishers, Dordrecht, The
Netherlands, 1995). Anomalous dispersion terms for Mn were included in
Fc. All nonhydrogen atoms were allowed to vibrate anisotropically.
All the hydrogen atoms were set in idealized positions (CH 0.96 Å;
U 1.2Ueq attached C) and held fixed during refinements. Distances
and angles for 3a are given in Tables S2 whereas final atomic
coordinates for nonhydrogen atoms, anisotropic temperature factors,
and atomic coordinates for hydrogen atoms are given in Table S3 to S5,
respectively. Distances and angles for 4a are given in Tables S6,
whereas final atomic coordinates for nonhydrogen atoms, anisotropic
temperature factors, and atomic coordinates for hydrogen atoms are
given in Table S7 to S9, respectively.
Table S1. Crystal data and structure refinement for complexes 3a and
4a.
Identification code 3a 4a
Empirical formula C28H17Co2MnO7 C30H17Co2MnO9
Formula weight 638.22 694.24
Temperature, K 160(2) 293(1)
Wavelength, Å 0.71073
Crystal system monoclinic triclinic
Space group P21/n (#14) P1 bar (#2)
a/Å 10.283(1) 9.464(1)
b/Å 18.334(3) 10.214(1)
c/Å 14.535(2) 14.691(2)
/° 81.41(1)
/° 109.42(2) 90.00(1)
/° 82.70(1)
Volume, Å3 2584(1) 1392.6(6)
Z 4 2
Density (calculated), Mg/m3 1.640 1.656
Absorption coefficient, mm1 1.795 1.679
F(000) 1280 696
range for data collection, ° 2.13 to 22.97 2.03 to 22.98
Index ranges 02sigma(I)] R1 0.0293 R1 0.0352,
wR2 0.0646 wR2 0.0885
R indices (all data) R1 0.1175 R1 0.0565
wR2 0.0809 wR2 0.0947
Largest diff. peak and hole, e.Å3 0.430 and 0.312 0.759 and 0.335
Table S2. Atomic coordinates (x 104) and equivalent isotropic
displacement parameters (Å2 x 103) for 3a. U(eq) is defined as one
third of the trace of the orthogonalized Uij tensor.
x y z U(eq)
Co(1) 7455(1) 1981(1) 8847(1) 34(1)
Co(2) 8289(1) 3175(1) 9563(1) 36(1)
Mn(1) 6017(1) 2651(1) 9781(1) 38(1)
O(1) 8345(4) 2761(2) 11626(3) 73(1)
O(2) 6216(4) 1072(2) 10132(3) 66(1)
O(3) 8735(6) 4632(2) 10440(3) 124(2)
O(4) 11023(4) 2553(2) 10533(3) 91(2)
O(5) 5882(4) 1198(2) 7097(3) 69(1)
O(6) 9594(4) 886(2) 9780(3) 78(1)
O(7) 9431(3) 2210(2) 7887(2) 50(1)
C(1) 7613(6) 2767(3) 10818(4) 49(1)
C(2) 6288(5) 1668(3) 9885(4) 45(1)
C(3) 8561(6) 4077(3) 10093(4) 58(2)
C(4) 9959(6) 2777(3) 10159(4) 55(2)
C(5) 6474(5) 1500(3) 7789(4) 41(1)
C(6) 8746(5) 1296(3) 9439(3) 44(1)
C(7) 8542(5) 2488(2) 8146(3) 36(1)
C(8) 8157(4) 3266(2) 8022(3) 32(1)
C(9) 6887(4) 3426(2) 8158(3) 32(1)
C(10) 6507(4) 2855(2) 8675(3) 31(1)
C(11) 6116(5) 4126(2) 7853(3) 32(1)
C(12) 6680(5) 4809(3) 8095(3) 40(1)
C(13) 5926(6) 5431(3) 7794(4) 51(1)
C(14) 4584(6) 5384(3) 7192(4) 58(2)
C(15) 3996(5) 4709(3) 6908(4) 54(2)
C(16) 4757(5) 4087(3) 7241(4) 43(1)
C(41) 3869(5) 2462(3) 9513(4) 53(2)
C(42) 4536(6) 2564(4) 10511(4) 63(2)
C(44) 4771(6) 3592(3) 9752(6) 75(2)
C(45) 4004(5) 3097(3) 9041(5) 61(2)
C(46) 3047(7) 1824(4) 9048(5) 99(2)
C(43) 5087(7) 3258(5) 10654(6) 86(2)
C(31) 8906(5) 3783(2) 7574(3) 36(1)
C(32) 8209(5) 4104(3) 6688(4) 47(1)
C(33) 8842(7) 4591(3) 6253(4) 57(2)
C(34) 10213(7) 4745(3) 6720(5) 66(2)
C(35) 10941(6) 4420(3) 7584(5) 63(2)
C(36) 10278(5) 3930(3) 8003(4) 52(1)
Table S3. Selected bond lengths [Å] and angles [°] for 3a.
Co(1)C(5) 1.769(5)
Co(1)C(6) 1.823(5)
Co(1)C(10) 1.849(4)
Co(1)C(7) 1.977(5)
Co(1)C(2) 2.292(5)
Co(1)Co(2) 2.4531(9)
Co(1)Mn(1) 2.6218(9)
Co(2)C(4) 1.801(6)
Co(2)C(3) 1.806(6)
Co(2)C(10) 1.949(4)
Co(2)C(9) 2.122(4)
Co(2)C(8) 2.205(4)
Co(2)C(1) 2.284(5)
Co(2)C(7) 2.500(5)
Co(2)Mn(1) 2.6418(9)
Mn(1)C(2) 1.821(5)
Mn(1)C(1) 1.835(6)
Mn(1)C(10) 1.876(4)
O(1)C(1) 1.164(6)
O(2)C(2) 1.161(5)
O(3)C(3) 1.123(6)
O(4)C(4) 1.125(6)
O(5)C(5) 1.132(5)
O(6)C(6) 1.133(5)
O(7)C(7) 1.212(5)
C(7)C(8) 1.475(6)
C(8)C(9) 1.415(6)
C(8)C(31) 1.499(6)
C(9)C(10) 1.416(6)
C(9)C(11) 1.497(6)
C(5)Co(1)C(6) 100.5(2)
C(5)Co(1)C(10) 101.1(2)
C(6)Co(1)C(10) 158.4(2)
C(5)Co(1)C(7) 92.5(2)
C(6)Co(1)C(7) 96.9(2)
C(10)Co(1)C(7) 83.44(19)
C(5)Co(1)C(2) 100.11(19)
C(6)Co(1)C(2) 88.60(19)
C(10)Co(1)C(2) 86.44(18)
C(7)Co(1)C(2) 165.16(18)
C(5)Co(1)Co(2) 146.32(16)
C(6)Co(1)Co(2) 108.50(16)
C(10)Co(1)Co(2) 51.56(13)
C(7)Co(1)Co(2) 67.73(13)
C(2)Co(1)Co(2) 97.46(13)
C(5)Co(1)Mn(1) 115.29(15)
C(6)Co(1)Mn(1) 121.74(14)
C(10)Co(1)Mn(1) 45.68(13)
C(7)Co(1)Mn(1) 124.02(14)
C(2)Co(1)Mn(1) 42.86(13)
Co(2)Co(1)Mn(1) 62.64(2)
C(4)Co(2)C(3) 100.3(2)
C(4)Co(2)C(10) 137.2(2)
C(3)Co(2)C(10) 122.4(2)
C(4)Co(2)C(9) 141.7(2)
C(3)Co(2)C(9) 99.9(2)
C(10)Co(2)C(9) 40.43(16)
C(4)Co(2)C(8) 104.3(2)
C(3)Co(2)C(8) 108.2(2)
C(10)Co(2)C(8) 67.85(17)
C(9)Co(2)C(8) 38.13(16)
C(4)Co(2)C(1) 88.7(2)
C(3)Co(2)C(1) 90.2(2)
C(10)Co(2)C(1) 87.79(19)
C(9)Co(2)C(1) 123.33(18)
C(8)Co(2)C(1) 154.70(18)
C(4)Co(2)Co(1) 89.18(17)
C(3)Co(2)Co(1) 168.67(19)
C(10)Co(2)Co(1) 48.00(12)
C(9)Co(2)Co(1) 75.80(11)
C(8)Co(2)Co(1) 75.03(11)
C(1)Co(2)Co(1) 83.70(13)
C(4)Co(2)C(7) 81.30(19)
C(3)Co(2)C(7) 140.3(2)
C(10)Co(2)C(7) 68.59(16)
C(9)Co(2)C(7) 62.60(16)
C(8)Co(2)C(7) 35.85(14)
C(1)Co(2)C(7) 129.47(16)
Co(1)Co(2)C(7) 47.03(10)
C(4)Co(2)Mn(1) 122.34(18)
C(3)Co(2)Mn(1) 107.42(19)
C(10)Co(2)Mn(1) 45.18(12)
C(9)Co(2)Mn(1) 81.29(12)
C(8)Co(2)Mn(1) 113.02(11)
C(1)Co(2)Mn(1) 42.99(14)
Co(1)Co(2)Mn(1) 61.81(2)
C(7)Co(2)Mn(1) 104.70(11)
C(2)Mn(1)C(1) 88.6(2)
C(2)Mn(1)C(10) 101.0(2)
C(1)Mn(1)C(10) 105.0(2)
C(2)Mn(1)Co(1) 58.87(15)
C(1)Mn(1)Co(1) 88.58(16)
C(10)Mn(1)Co(1) 44.84(13)
C(2)Mn(1)Co(2) 104.65(16)
C(1)Mn(1)Co(2) 58.05(16)
C(10)Mn(1)Co(2) 47.46(13)
Co(1)Mn(1)Co(2) 55.55(2)
O(1)C(1)Mn(1) 158.2(5)
O(1)C(1)Co(2) 122.8(4)
Mn(1)C(1)Co(2) 79.0(2)
O(2)C(2)Mn(1) 159.1(4)
O(2)C(2)Co(1) 122.7(4)
Mn(1)C(2)Co(1) 78.27(18)
O(3)C(3)Co(2) 178.7(5)
O(4)C(4)Co(2) 177.5(5)
O(5)C(5)Co(1) 177.5(5)
O(6)C(6)Co(1) 176.2(4)
O(7)C(7)C(8) 124.7(4)
O(7)C(7)Co(1) 125.2(4)
C(8)C(7)Co(1) 110.1(3)
O(7)C(7)Co(2) 139.8(3)
C(8)C(7)Co(2) 61.1(2)
Co(1)C(7)Co(2) 65.23(13)
C(9)C(8)C(7) 113.9(4)
C(9)C(8)C(31) 124.2(4)
C(7)C(8)C(31) 120.6(4)
C(9)C(8)Co(2) 67.7(2)
C(7)C(8)Co(2) 83.0(3)
C(31)C(8)Co(2) 128.4(3)
C(8)C(9)C(10) 110.6(4)
C(8)C(9)C(11) 123.9(4)
C(10)C(9)C(11) 125.4(4)
C(8)C(9)Co(2) 74.1(2)
C(10)C(9)Co(2) 63.2(2)
C(11)C(9)Co(2) 126.5(3)
C(9)C(10)Co(1) 119.1(3)
C(9)C(10)Mn(1) 143.3(3)
Co(1)C(10)Mn(1) 89.48(18)
C(9)C(10)Co(2) 76.4(3)
Co(1)C(10)Co(2) 80.44(17)
Mn(1)C(10)Co(2) 87.36(17)
Table S4. Anisotropic displacement parameters (Å2 x 103) for 3a. The
anisotropic
displacement factor exponent takes the form: 22[ h2a*2U11 + ... + 2
h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
Co(1) 41(1) 30(1) 34(1) 0(1) 15(1) 2(1)
Co(2) 38(1) 34(1) 35(1) 4(1) 12(1) 1(1)
Mn(1) 43(1) 37(1) 40(1) 1(1) 23(1) 1(1)
O(1) 74(3) 101(3) 36(2) 2(2) 9(2) 18(3)
O(2) 95(3) 45(2) 81(3) 15(2) 60(3) 0(2)
O(3) 209(6) 44(3) 70(3) 22(2) 16(3) 3(3)
O(4) 51(3) 112(4) 87(3) 9(3) 6(3) 29(3)
O(5) 72(3) 62(3) 57(3) 13(2) 1(2) 4(2)
O(6) 91(3) 79(3) 65(3) 21(2) 27(2) 47(3)
O(7) 57(2) 36(2) 69(2) 0(2) 39(2) 7(2)
C(1) 62(4) 43(3) 49(3) 4(3) 28(3) 2(3)
C(2) 52(3) 50(4) 42(3) 4(3) 26(3) 1(3)
C(3) 73(4) 49(4) 40(3) 1(3) 2(3) 1(3)
C(4) 54(4) 61(4) 46(3) 11(3) 14(3) 1(3)
C(5) 46(3) 35(3) 44(3) 3(3) 20(3) 4(3)
C(6) 53(4) 45(3) 39(3) 3(3) 23(3) 6(3)
C(7) 34(3) 35(3) 37(3) 7(2) 10(2) 3(2)
C(8) 32(3) 32(3) 31(3) 1(2) 10(2) 2(2)
C(9) 31(3) 29(3) 32(3) 2(2) 7(2) 2(2)
C(10) 32(3) 29(3) 32(3) 1(2) 11(2) 4(2)
C(11) 37(3) 32(3) 32(3) 5(2) 17(2) 5(2)
C(12) 37(3) 39(3) 47(3) 3(3) 19(3) 4(3)
C(13) 68(4) 28(3) 67(4) 4(3) 38(4) 3(3)
C(14) 62(4) 49(4) 73(4) 17(3) 37(4) 21(3)
C(15) 42(3) 72(4) 47(4) 15(3) 14(3) 15(3)
C(16) 43(3) 40(3) 46(3) 2(3) 16(3) 2(3)
C(41) 46(3) 56(4) 65(4) 5(3) 28(3) 5(3)
C(42) 49(4) 100(5) 54(4) 14(4) 35(3) 10(4)
C(44) 68(5) 57(4) 122(6) 10(4) 59(5) 16(4)
C(45) 44(4) 72(4) 78(4) 18(4) 36(3) 18(3)
C(46) 75(5) 107(6) 118(6) 13(5) 34(4) 0(5)
C(43) 61(4) 126(7) 84(6) 55(5) 42(4) 4(5)
C(31) 49(3) 28(3) 39(3) 1(2) 26(3) 0(2)
C(32) 58(4) 40(3) 49(3) 1(3) 28(3) 4(3)
C(33) 80(5) 42(3) 65(4) 13(3) 44(4) 8(3)
C(34) 95(5) 45(4) 87(5) 5(4) 67(4) 4(4)
C(35) 57(4) 66(4) 78(5) 5(4) 38(4) 22(3)
C(36) 44(3) 58(4) 58(4) 5(3) 23(3) 5(3)
Table S5. Hydrogen coordinates (x 104) and isotropic displacement
parameters (Å2 x 103)
for 4a.
x y z U(eq)
H(12) 7604 4848 8476 48
H(13) 6322 5884 7998 61
H(14) 4072 5806 6975 69
H(15) 3089 4674 6493 65
H(16) 4352 3633 7053 51
H(42) 4598 2222 10996 76
H(44) 5023 4061 9637 90
H(45) 3650 3181 8372 73
H(46A) 3153 1740 8425 149
H(46B) 3357 1404 9455 149
H(46C) 2093 1913 8960 149
H(43) 5583 3465 11252 103
H(32) 7286 3988 6376 56
H(33) 8358 4809 5661 69
H(34) 10654 5079 6442 80
H(35) 11870 4527 7888 76
H(36) 10774 3698 8582 63
Table S6. Atomic coordinates (x 104) and equivalent isotropic
displacement parameters (Å2 x 103) for complex 4a. U(eq) is defined as
one third of the trace of the orthogonalized Uij tensor.
x y z U(eq)
Co(1) 4197(1) 3762(1) 2981(1) 35(1)
Co(2) 1882(1) 4564(1) 3351(1) 36(1)
Mn(1) 505(1) 690(1) 2856(1) 39(1)
O(1) 1455(4) 2672(4) 4292(3) 93(1)
O(2) 739(3) 2318(3) 1380(2) 65(1)
O(3) 1873(3) 890(3) 4202(2) 57(1)
O(4) 5951(3) 2024(3) 1839(3) 74(1)
O(5) 5967(4) 6300(3) 2809(3) 82(1)
O(6) 4894(4) 3107(4) 4797(3) 92(1)
O(7) 1032(3) 4864(4) 2826(2) 74(1)
O(8) 1602(4) 3941(4) 5246(2) 86(1)
O(9) 2977(4) 7423(3) 3684(2) 71(1)
C(1) 1034(5) 1929(4) 3714(3) 56(1)
C(2) 658(4) 1700(4) 1966(3) 47(1)
C(3) 1354(4) 1033(4) 3491(3) 38(1)
C(4) 5256(4) 2670(4) 2284(3) 48(1)
C(5) 5304(4) 5330(4) 2897(3) 47(1)
C(6) 4619(4) 3347(4) 4097(3) 52(1)
C(7) 88(5) 4740(4) 3049(3) 48(1)
C(8) 1689(5) 4181(4) 4523(3) 53(1)
C(9) 2561(4) 6321(4) 3559(3) 45(1)
C(10) 1736(3) 1444(3) 2624(2) 31(1)
C(11) 2216(3) 2857(3) 2639(2) 31(1)
C(12) 2586(4) 3849(3) 2142(2) 33(1)
C(21) 2338(4) 632(4) 3230(3) 50(1)
C(22) 1067(5) 1026(4) 3526(3) 56(1)
C(23) 250(5) 1372(4) 2748(4) 62(1)
C(24) 971(5) 1174(4) 1978(4) 65(1)
C(25) 2271(5) 716(4) 2271(3) 57(1)
C(26) 3542(5) 271(5) 3840(4) 75(2)
C(31) 2414(4) 490(3) 1933(2) 35(1)
C(32) 3218(4) 416(4) 2218(3) 45(1)
C(33) 3864(5) 1282(4) 1580(4) 63(1)
C(34) 3736(6) 1235(5) 662(4) 74(2)
C(35) 2948(5) 337(5) 369(3) 70(1)
C(36) 2279(4) 521(4) 992(3) 51(1)
C(41) 2572(4) 4251(3) 1221(2) 36(1)
C(42) 1818(5) 5238(5) 1035(3) 58(1)
C(43) 1792(5) 5578(5) 157(4) 72(1)
C(44) 2520(6) 4948(6) 538(3) 71(1)
C(45) 3282(7) 3986(6) 358(3) 89(2)
C(46) 3319(6) 3640(5) 514(3) 69(1)
Table S7. Selected Bond lengths [Å] and angles [°] for 4a.
Co(1)C(4) 1.801(5)
Co(1)C(6) 1.810(5)
Co(1)C(5) 1.819(4)
Co(1)C(12) 1.980(3)
Co(1)C(11) 2.011(3)
Co(1)Co(2) 2.4678(7)
Co(2)C(7) 1.792(5)
Co(2)C(9) 1.808(4)
Co(2)C(8) 1.826(5)
Co(2)C(11) 1.957(3)
Co(2)C(12) 1.967(3)
Mn(1)C(1) 1.769(5)
Mn(1)C(2) 1.799(5)
Mn(1)C(3) 1.958(4)
Mn(1)C(10) 2.207(3)
O(1)C(1) 1.157(5)
O(2)C(2) 1.148(5)
O(3)C(3) 1.192(4)
O(4)C(4) 1.129(5)
O(5)C(5) 1.128(5)
O(6)C(6) 1.131(5)
O(7)C(7) 1.137(5)
O(8)C(8) 1.125(5)
O(9)C(9) 1.132(5)
C(3)C(10) 1.431(5)
C(10)C(11) 1.454(5)
C(10)C(31) 1.502(5)
C(11)C(12) 1.346(5)
C(12)C(41) 1.473(5)
C(4)Co(1)C(6) 98.60(19)
C(4)Co(1)C(5) 97.75(18)
C(6)Co(1)C(5) 105.65(19)
C(4)Co(1)C(12) 102.68(16)
C(6)Co(1)C(12) 142.78(16)
C(5)Co(1)C(12) 101.33(17)
C(4)Co(1)C(11) 101.22(16)
C(6)Co(1)C(11) 106.62(16)
C(5)Co(1)C(11) 139.31(16)
C(12)Co(1)C(11) 39.41(14)
C(4)Co(1)Co(2) 150.43(13)
C(6)Co(1)Co(2) 98.48(13)
C(5)Co(1)Co(2) 100.63(13)
C(12)Co(1)Co(2) 51.05(10)
C(11)Co(1)Co(2) 50.56(10)
C(7)Co(2)C(9) 97.49(18)
C(7)Co(2)C(8) 101.96(19)
C(9)Co(2)C(8) 101.59(18)
C(7)Co(2)C(11) 104.11(16)
C(9)Co(2)C(11) 142.71(16)
C(8)Co(2)C(11) 103.16(16)
C(7)Co(2)C(12) 100.56(16)
C(9)Co(2)C(12) 106.48(16)
C(8)Co(2)C(12) 141.05(17)
C(11)Co(2)C(12) 40.13(14)
C(7)Co(2)Co(1) 151.62(13)
C(9)Co(2)Co(1) 96.13(13)
C(8)Co(2)Co(1) 99.51(14)
C(11)Co(2)Co(1) 52.53(10)
C(12)Co(2)Co(1) 51.54(10)
C(1)Mn(1)C(2) 92.3(2)
C(1)Mn(1)C(3) 86.10(18)
C(2)Mn(1)C(3) 113.64(16)
C(1)Mn(1)C(10) 103.16(16)
C(2)Mn(1)C(10) 77.33(14)
C(3)Mn(1)C(10) 39.63(14)
C(24)Mn(1)C(10) 106.78(15)
C(23)Mn(1)C(10) 97.36(15)
C(22)Mn(1)C(10) 121.75(15)
C(25)Mn(1)C(10) 142.93(16)
C(21)Mn(1)C(10) 159.33(15)
O(1)C(1)Mn(1) 175.1(4)
O(2)C(2)Mn(1) 178.0(4)
O(3)C(3)C(10) 141.1(4)
O(3)C(3)Mn(1) 139.2(3)
C(10)C(3)Mn(1) 79.6(2)
O(4)C(4)Co(1) 177.5(4)
O(5)C(5)Co(1) 177.1(4)
O(6)C(6)Co(1) 178.9(4)
O(7)C(7)Co(2) 177.5(4)
O(8)C(8)Co(2) 178.5(4)
O(9)C(9)Co(2) 179.4(4)
C(3)C(10)C(11) 116.4(3)
C(3)C(10)C(31) 117.8(3)
C(11)C(10)C(31) 116.5(3)
C(3)C(10)Mn(1) 60.77(19)
C(11)C(10)Mn(1) 122.1(2)
C(31)C(10)Mn(1) 111.7(2)
C(12)C(11)C(10) 146.7(3)
C(12)C(11)Co(2) 70.3(2)
C(10)C(11)Co(2) 138.2(2)
C(12)C(11)Co(1) 69.1(2)
C(10)C(11)Co(1) 125.3(2)
Co(2)C(11)Co(1) 76.90(12)
C(11)C(12)C(41) 145.4(3)
C(11)C(12)Co(2) 69.5(2)
C(41)C(12)Co(2) 134.3(3)
C(11)C(12)Co(1) 71.5(2)
C(41)C(12)Co(1) 130.6(2)
Co(2)C(12)Co(1) 77.41(13
Table S8. Anisotropic displacement parameters (Å2 x 103) for 4a. The
anisotropic
displacement factor exponent takes the form: 22[ h2a*2U11 + ... + 2
h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
Co(1) 31(1) 40(1) 34(1) 4(1) 2(1) 1(1)
Co(2) 39(1) 37(1) 31(1) 1(1) 4(1) 6(1)
Mn(1) 33(1) 39(1) 42(1) 7(1) 5(1) 2(1)
O(1) 94(3) 71(2) 101(3) 15(2) 58(2) 3(2)
O(2) 56(2) 74(2) 67(2) 30(2) 15(2) 1(2)
O(3) 63(2) 75(2) 34(2) 18(2) 8(1) 0(2)
O(4) 52(2) 77(2) 92(3) 3(2) 21(2) 20(2)
O(5) 74(2) 60(2) 105(3) 12(2) 14(2) 17(2)
O(6) 90(3) 135(3) 56(2) 34(2) 20(2) 16(2)
O(7) 50(2) 99(3) 75(2) 1(2) 3(2) 28(2)
O(8) 135(3) 87(3) 38(2) 14(2) 22(2) 20(2)
O(9) 87(2) 41(2) 84(2) 9(2) 8(2) 2(2)
C(1) 47(2) 54(3) 64(3) 8(2) 19(2) 7(2)
C(2) 28(2) 53(3) 56(3) 3(2) 6(2) 1(2)
C(3) 45(2) 35(2) 34(2) 3(2) 2(2) 4(2)
C(4) 34(2) 54(3) 54(3) 6(2) 4(2) 0(2)
C(5) 39(2) 46(3) 53(3) 4(2) 5(2) 1(2)
C(6) 41(2) 62(3) 53(3) 12(2) 5(2) 2(2)
C(7) 49(3) 51(2) 43(2) 2(2) 11(2) 10(2)
C(8) 68(3) 46(3) 43(3) 2(2) 8(2) 9(2)
C(9) 55(3) 43(3) 39(2) 4(2) 1(2) 11(2)
C(10) 29(2) 35(2) 28(2) 5(2) 0(2) 3(2)
C(11) 30(2) 36(2) 26(2) 2(2) 0(2) 5(2)
C(12) 31(2) 36(2) 30(2) 3(2) 2(2) 4(2)
C(21) 40(2) 48(2) 60(3) 16(2) 2(2) 11(2)
C(22) 54(3) 48(3) 65(3) 24(2) 2(2) 12(2)
C(23) 49(3) 33(2) 103(4) 14(2) 6(3) 1(2)
C(24) 65(3) 50(3) 68(3) 7(2) 17(3) 16(2)
C(25) 51(3) 54(3) 60(3) 11(2) 9(2) 17(2)
C(26) 58(3) 82(4) 81(4) 17(3) 13(3) 12(3)
C(31) 30(2) 36(2) 37(2) 3(2) 3(2) 4(2)
C(32) 42(2) 41(2) 52(2) 7(2) 4(2) 3(2)
C(33) 49(3) 43(3) 95(4) 5(3) 19(3) 10(2)
C(34) 78(4) 56(3) 80(4) 16(3) 32(3) 9(3)
C(35) 83(4) 79(4) 40(3) 14(2) 16(2) 3(3)
C(36) 53(3) 60(3) 37(2) 1(2) 5(2) 8(2)
C(41) 38(2) 36(2) 32(2) 8(2) 0(2) 4(2)
C(42) 65(3) 66(3) 49(3) 23(2) 4(2) 17(2)
C(43) 74(3) 82(4) 66(3) 39(3) 11(3) 8(3)
C(44) 81(3) 90(4) 45(3) 31(3) 6(3) 9(3)
C(45) 131(5) 107(5) 41(3) 28(3) 29(3) 38(4)
C(46) 94(4) 82(3) 43(3) 23(2) 20(3) 38(3)
Table S9. Hydrogen coordinates (x 104) and isotropic displacement
parameters (Å2 x 103)
for 4a.
x y z U(eq)
H(22) 809 1052 4133 67
H(23) 631 1683 2753 75
H(24) 661 1316 1375 77
H(25) 2966 506 1889 68
H(26A) 4037 357 3582 113
H(26B) 4189 1060 3888 113
H(26C) 3172 123 4441 113
H(32) 3327 446 2843 54
H(33) 4388 1900 1781 75
H(34) 4181 1809 237 89
H(35) 2862 304 258 84
H(36) 1738 1119 784 61
H(42) 1317 5685 1502 69
H(43) 1268 6249 41 86
H(44) 2493 5176 1127 85
H(45) 3790 3550 826 107
H(46) 3860 2980 625 83
‡ On sabbatical leave from: Department of Chemistry, McMaster
University, Hamilton, Ont., Canada L8S 4M1
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