Supporting Information

Chemical and Structural Effects of Bulkness on Bent-Phosphinidene Bridges: Synthesis and Reactivity of the Diiron Complex [Fe2Cp2{P(2,4,6-C6H2tBu3)}(-CO)(CO)2].

M. Angeles Alvarez, M. Esther Garca, Roco Gonzlez, Alberto Ramos and Miguel A. Ruiz* Departamento de Qumica Orgnica e Inorgnica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.

Preparative Procedures, Spectroscopic and Microanalytical Data for New Compounds. Structure Solution and Refinements for compounds 3 and 5T

General Procedures and Starting Materials. All manipulations and reactions were carried out under a nitrogen (99.995%) atmosphere using standard Schlenk techniques. Solvents were purified according to literature procedures, and distilled prior to use.1 Petroleum ether refers to that fraction distilling in the range 338-343 K. The phosphine PR*H2 (R* = 2,4,6-C6H2tBu3),2 and the complexes [FeCp2]BF4,3 [Fe2Cp2(CO)2(CO)(NCMe)],4 were prepared as described previously, the latter being prepared in situ and used without further purification; all other reagents were obtained from the usual commercial suppliers and used as received, unless otherwise stated. Photochemical experiments were performed using jacketed quartz Schlenk tubes, cooled by tap water (ca. 285 K). A 400 W mercury lamp (Applied Photophysics) placed ca. 1 cm away from the Schlenk tube was used for these experiments. Chromatographic separations were carried out using jacketed columns cooled by tap water. Commercial aluminum oxide (activity I, 150 mesh) was degassed under vacuum prior to use. The latter was afterwards mixed under nitrogen with the appropriate amount of water to reach the activity desired. Filtrations were performed using diatomaceous earth or with a cannula. IR stretching frequencies of CO ligands were measured in solution, are referred to as (CO) (solvent), and are given in cm1. Nuclear Magnetic Resonance (NMR) spectra were routinely recorded in CD2Cl2 solutions at 300.13 (1H), 121.50 (31P{1H}) or 75.47 MHz (13C{1H}), at 290 K unless otherwise stated. Chemical shifts () are given in ppm, relative to internal tetramethylsilane (1H,
13

C) or external 85%

aqueous H3PO4 solutions (31P). Coupling constants (J) are given in Hertz.

Preparative Procedures, Spectroscopic and Microanalytical Data for the New Compounds. Preparation of [Fe2Cp2(-CO)2(CO)(PR*H2)] (1). An acetonitrile solution (50 mL) of [Fe2Cp2(-CO)2(CO)(NCMe)] was prepared in situ from [Fe2Cp2(CO)4] (1.000 g, 2.825 mmol; reaction time ca. 4 h at 263 K), and was filtered with a cannula. The solvent was then removed under vacuum from the filtrate, and the residue was dissolved in dichloromethane (20 ml) and stirred with PR*H2 (0.787 g, 2.827 mmol) at room temperature for 10 min to give a dark green solution. The solvent was then

removed in vacuum and the residue was washed with petroleum ether (6 x 10 mL) to give compound 1 as a dark-green microcrystalline solid. The petroleum ether fractions were collected and the solvent removed under vacuum. The residue was then dissolved in dichloromethane-petroleum ether (1:18) and chromatographed on alumina (activity IV). Elution with dichloromethane-petroleum ether (1:14) gave a red fraction containing some [Fe2Cp2(CO)4] and then a green fraction which yielded, after removal of solvents, a second crop of compound 1 (combined yield: 1.520 g, 89 %). This complex exists in solution as an equilibrium mixture of the corresponding trans and cis isomers. Anal. Calcd for C31H41Fe2O3P: C, 61.61; H, 6.84. Found: C, 61.49; H, 6.88. (CO) (CH2Cl2): 1936 (m), 1772 (w), 1732 (vs). Spectroscopic data for trans-1: 1H NMR (400.13 MHz):

7.45 (s, 2H, C6H2), 4.71 (s, 5H, Cp), 4.44 (d, JHP = 343, 2H, PH), 3.99 (s, 5H, Cp),
1.59 (s, 18H, o-tBu), 1.31 (s, 9H, p-tBu).
31

P{1H} NMR (162.00 MHz): 21.3.

Spectroscopic data for cis-1: 1H NMR (400.13 MHz): 4.71 (s, 5H, Cp), 4.51 (d, JHP = 343, 2H, PH), 3.94 (s, 5H, Cp), 1.65 (s, 18H, o-tBu); other resonances of this isomer were obscured by those of the major isomer; ratio trans/cis = 5. 31P{1H} NMR (162.00 MHz): 21.3. Preparation of [Fe2Cp2(-PR*H)(-CO)(CO)2]BF4 (2). Solid [FeCp2]BF4 (0.400 g, 1.467 mmol) was slowly added to a stirred suspension of NaHCO3 (1.0 g, 11.9 mmol) in a dichloromethane solution (30 mL) of compound 1 (0.400 g, 0.662 mmol) at 243 K, and the mixture was further stirred for 2 h at the same temperature to give a red solution which was filtered with a cannula. Removal of the solvent under vacuum from the filtrate and washing of the residue with petroleum ether (7 x 8 mL) gave compound 2 as a red microcrystalline solid (0.420 g, 92 %). Anal. Calcd for C31H40BF4Fe2O3P: C, 53.95; H, 5.84. Found: C, 54.00; H, 5.88. (CO) (CH2Cl2): 2028 (vs), 2000 (w), 1825 (m). 1H NMR (400.13 MHz): 9.88 (d, JHP = 385, 1H, PH), 7.08 (s, 2H, C6H2), 5.32

(s, 10H, Cp), 1.64 (s, 18H, o-tBu), 1.06 (s, 9H, p-tBu). 31P{1H} NMR (162.00
MHz): 181.7. Preparation of [Fe2Cp2(-PR*)(-CO)(CO)2] (3). Solid KOH (ca. 0.1 g, excess), was added to a dichloromethane solution (6 mL) of compound 2 (0.050 g, 0.072 mmol) at room temperature, and the mixture was vigorously stirred for 5 min to give a winered solution which was filtered using a cannula. Solvent was then removed under

vacuum from the filtrate and the residue was washed with petroleum ether (2 x 5 mL) to give compound 3 as a dark red, air-sensitive microcrystalline solid (0.042 g, 95 %). The crystals used in the X-ray diffraction study were grown by the slow diffusion of a layer of petroleum ether into a saturated solution of the compound in toluene at 253 K. (CO) (CH2Cl2): 1991 (vs), 1958 (w), 1769 (m). 1H NMR: 6.92 (s, 2H, C6H2), 4.86 (s,

10H, Cp), 1.58 (s, 18H, o-tBu), 1.07 (s, 9H, p-tBu).31P{1H} NMR: 593.4.
Preparation of [Fe2Cp2(-CO)2(CO){PH(CH2CMe2)C6H2tBu2}] (4). A toluene solution (5 mL) of compound 1 (0.050 g, 0.083 mmol) was placed in a Schlenk tube equipped with a Youngs valve, and it was stirred at 338 K for 1h to give a brown-green mixture. The solvent was then removed under vacuum and the residue was dissolved in a minimum of dichloromethane-petroleum ether (1:6) and chromatographed on alumina (activity IV) at 288 K. Elution with dichloromethane-petroleum ether (1:4) gave a red fraction containing the dimer [Fe2Cp2(CO)4]. Elution with dichloromethane-petroleum ether (4:1) gave a green fraction yielding, after removal of solvents, compound 4 as a dark green microcrystalline solid (0.036 g, 71%). This complex exists in solution as an equilibrium mixture of the corresponding trans and cis isomers. Anal. Calcd for C31H39Fe2O3P: C, 61.82; H, 6.53. Found: C, 61.67; H, 6.51. (CO) (CH2Cl2): 1934 (m), 1772 (w), 1730 (vs). Spectroscopic data for trans-4:
1

H NMR (C6D6): 7.48, 7.06

(2m, 2 x 1H, C6H2), 4.56 (dd, JHP = 348, JHH = 5, 1H, PH), 4.47, 4.09 (2s, 2 x 5H, Cp), 2.53, 1.99 (2m, 2 x 1H, CH2), 1.66 (s, 3H, Me), 1.64 (s, 9H, o-tBu), 1.20 (s, 9H, p-tBu), 1.00 (s, 3H, Me). 31P{1H} NMR (C6D6): 36.8. Spectroscopic data
for cis-4: 1H NMR (C6D6): 4.51, 4.20 (2 x s, 2 x 5H, Cp); other resonances of this isomer were obscured by those of the major isomer; ratio trans/cis = 5. 31P{1H} NMR (C6D6): 37.5. Preparation of [Fe2Cp2{P(O)R*}(CO)3] (5). A dichloromethane solution (10 mL) of compound 3 (0.100 g, 0.188 mmol) was stirred in contact with air at room temperature for 10 min to give a red solution shown (by IR) to contain the isomer 5B as the major species in solution. Upon further stirring at room temperature for 1.5 h, a brown solution was then obtained and shown (by IR and NMR) to be an equilibrium mixture of the isomers 5B and 5T. The latter in turn exists in solution as an equilibrium mixture of cis and trans isomers. After removal of solvent under vacuum, the residue

was dissolved in a minimum of dichloromethane-petroleum ether (1/6) and chromatographed on an alumina column (activity IV) at 263 K. Elution with the same solvent mixture gave a red fraction containing the dimer [Fe2Cp2(CO)4]. Elution with dichloromethane-petroleum ether (2:1) gave a brown fraction containing initially the isomers trans- and cis-5T, but the equilibrium mixture with the isomer 5B is reached in ca. 20 min at room temperature after collection. Finally, elution with tetrahydrofurandichloromethane (1:1) gave a red fraction containing initially the isomer 5B, although the equilibrium mixture with the isomers 5T is reached in ca. 1 h. These two fractions were joined and the solvent was removed under vacuum to give a red solid containing a mixture of the three isomers of compound 5 (0.063 g, 61%). The equilibrium ratio 5T/5B is ca. 10:1 in either C6D6 or CD2Cl2 at room temperature. The equilibrium ratio trans-5T/cis-5T is ca. 5:1 in C6D6 and 8:5 in CD2Cl2 at 293 K. This ratio was also temperature-dependent in the latter solvent, it being ca. 6:5 at 253 K, 1:1 at 233 K and 5:7 at 213 K The crystals used in the X-ray diffraction study were grown from a concentrated petroleum ether solution of the compound at 253 K and correspond to the isomer trans-5T. Anal. Calcd for C31H39Fe2O4P: C, 60.22; H, 6.36. Found: C, 60.19; H, 6.35. Spectroscopic data for isomer 5B: (CO) (CH2Cl2): 1997 (vs), 1965 (w), 1774 (m). 31P{1H} NMR (161.98 MHz): 312.0. 1H NMR (400.13 MHz): 6.94 (d, JHP =

3, 2H, C6H2), 4.93 (s, 10H, Cp), 1.70 (s, 18H, o-tBu), 1.02 (s, 9H, p-tBu). 13C{1H}
NMR (100.61 MHz, 233 K): 209.8 (d, JCP = 14, FeCO), 122.1 [d, JCP = 13,

C3(C6H2)], 91.3 (s, Cp), 30.8 [s, C2(tBu)]; other resonances of this isomer were
obscured by those of the major isomers. Spectroscopic data for isomers 5T: (CO) (CH2Cl2): 1985 (m, isomer cis), 1964 (m, isomer trans), 1802 (w), 1769 (vs).
31

P{1H} NMR (161.98 MHz): 432.8 (s, trans and cis).1H NMR (400.13 MHz):

7.42 (d, JHP =2, 2H, C6H2), 4.98 (s, br, 5H, Cp, trans), 4.86 (s, br, 5H, Cp, cis), 4.20 (s, 5H, Cp, trans and cis), 1.66 (s, br, 18H, o-tBu), 1.34 (s, 9H, p-tBu).
31

P{1H} NMR (161.98 MHz, 233 K): 432.5 (s, trans), 432.3 (s, cis). 1H NMR

(400.13 MHz, 233 K, isomer trans): 7.42 (s, 2H, C6H2), 5.01 (s, 5H, Cp), 4.20 (s,

5H, Cp), 1.67 (s, 18H, o-tBu), 1.34 (s, 9H, p-tBu). 1H NMR (400.13 MHz, 233 K,
isomer cis): 7.41 (s, 2H, C6H2), 4.87 (s, 5H, Cp), 4.23 (s, 5H, Cp), 1.60 (s, 18H,

o-tBu), 1.34 (s, 9H, p-tBu). 13C{1H} NMR (100.62 MHz, 233 K, isomer trans):

272.4 (d, JCP = 15, 2 x -CO), 211.5 (d, JCP = 4, FeCO), 152.5 [s, C4(C6H2)], 148.8 [d, JCP = 11, C1(C6H2)], 147.8 [d, JCP = 6, C2(C6H2)], 122.5 [d, JCP = 6, C3(C6H2)], 91.2, 89.6 (2s, Cp), 38.7 [s, o-C1(tBu)], 34.2 [s, p-C1(tBu)], 33.7 [s, oC2(tBu)], 31.1 [s, p-C2(tBu)]. 13C{1H} NMR (100.62 MHz, 233 K, isomer cis): 273.2 (d, JCP = 16, 2 x -CO), 211.9 (s, FeCO), 152.3 [s, C4(C6H2)], 149.6 [d, JCP = 13, C1(C6H2)], 147.3 [d, JCP = 6, C2(C6H2)], 122.7 [d, JCP = 6, C3(C6H2)], 90.8, 89.0 (2s, Cp), 38.9 [s, o-C1(tBu)], 35.4 [s, p-C1(tBu)], 34.0 [s, o-C2(tBu)], 31.1 [s, p-C2(tBu)].

X-ray Structure Determination of Compounds 3 and 5T. The X-ray intensity data were collected on a Kappa-Appex-II Bruker diffractometer using graphitemonochromated MoK radiation at 100 K. The software APEX5 was used for collecting frames with the omega/phi scans measurement method. In the case of 5T twinning was found to occur in the crystal, and the program Cell Now6 was used to determine the twin law, the cell dimensions and orientation matrixes. The Bruker SAINT,7 software was used for the data reduction, and a multi-scan absorption correction was applied with SADABS.8 Using the program suite WinGX,9 the structure was solved by Patterson interpretation and phase expansion, and refined with full-matrix least squares on F2 using SHELXL97.10 In the case of 3 all non-hydrogen atoms were refined anisotropically, and all hydrogen atoms were fixed at calculated positions and were given an overall isotropic thermal parameter. In the case of 5T, one of the ciclopentadienyl groups was found to be disordered in two positions, and could be satisfactorily modelled with occupancy factors of 0.5 at each position. All positional parameters and anisotropic temperature factors for all non-H atoms were refined anisotropically except for the carbon atoms involved in the disorder, which were refined isotropically to prevent their temperature factors from becoming non-positive definite. All hydrogen atoms were geometrically placed and refined using a riding model.

References (1) Armarego, W. L. F.; Chai, C. Purification of Laboratory Chemicals, 5th Edition; Butterworth-Heinemann: Oxford, U.K., 2003.

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Cowley, A. H.; Norman, N. C.; Pakulski, M. Inorg. Synth. 1990, 27, 253. Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877. Labinger, J. A.; Madhaven, S. J. Organomet. Chem. 1977, 134, 381. APEX 2, version 2.0-1; Bruker AXS Inc: Madison, WI, 2005. Sheldrick, G. M. University of Gottingen: Germany, Ver 2008/2. SMART & SAINT Software Reference Manuals, Version 5.051 (Windows NT Version); Bruker Analytical X-ray Instruments: Madison, WI, 1998.

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Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction; University of Gttingen: Gttingen, Germany, 1996.

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Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837. Sheldrick, G. M. Acta Crystallogr., Sect. A 2008, 64, 112.