Supporting Information

High-Yield Synthesis and Reactivity of Stable Diiron Complexes with Bent-Phosphinidene Bridges
Celedonio M. Alvarez, M. Angeles Alvarez, M. Esther Garca, Roco Gonzlez, Miguel A. Ruiz,* Hayrullo Hamidov and John C. Jeffery.

Departamento de Qumica Orgnica e Inorgnica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain. School of Chemistry, University of Bristol, Bristol BS8 1TS, UK.

Preparative Procedures and Spectroscopic Data for New Compounds. Structure Solution and Refinements for compounds 3b and 5a CIF file for compounds 3b and 5a.

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. Petroleum ether refers to that fraction distilling in the range 65-70 C. Compounds [FeCp2]BF4,1 and [Fe2Cp2(CO)2(CO)(CNMe)],2 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 mixed under nitrogen with the appropriate amount of water to reach the activity desired. Filtrations were performed using diatomaceous earth. IR stretching frequencies of CO ligands were measured in solution, are referred to as (CO) (solvent), and are given in cm-1. Nuclear Magnetic Resonance (NMR) spectra were routinely recorded in solution 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 (TMS) or external 85% aqueous H3PO4 solutions (31P). Coupling constants (J) are given in Hertz.

Preparative Procedures For New Compounds

Preparation of trans-[Fe2Cp2(-CO)2(CO)(PCyH2)] (1a). An acetonitrile solution (20 mL) of [Fe2Cp2(-CO)2(CO)(CNMe)] was prepared in situ from [Fe2Cp2(CO)4] (0.300 g, 0.848 mmol). The solvent was then removed under vacuum and the residue dissolved in dichloromethane (20 ml) and stirred with PCyH2 (114 L, 0.857 mmol) at room temperature for 5 min to give a dark green solution which was filtered. Solvent was then removed in vacuum from the filtrate and the residue was washed with petroleum ether (3 x 10 mL) to give compound 1a as a dark-green microcrystalline solid (0.335 g, 89 %). Anal. Calcd for C19H23Fe2O3P: C, 51.62; H, 5.24. Found: C, 51.23; H, 2

5.05. (CO) (CH2Cl2): 1935 (s), 1770 (w), 1730 (vs). 1H NMR (CDCl3) 4.72 (s, 5H, Cp), 4.50 (d, JHP = 1, 5H, Cp), 3.28 (dd, JHP = 327, JHH = 6, 2H, PH), 2.05-0.97 (m, 11H, Cy). 31P{1H} NMR (CDCl3) 17.2. Preparation of trans-[Fe2Cp2(-CO)2(CO)(PPhH2)] (1b). The procedure is completely analogous to that described for 1a, but using PPhH2 instead. By starting from [Fe2Cp2(CO)4] (0.500 g, 1.411 mmol) and using 156 L of PPhH2 (1.418 mmol), compound 1b was obtained as a dark-green microcrystalline solid (0.536 g, 87 %). Anal. Calcd for C19H17Fe2O3P: C, 52.34; H, 3.93. Found: C, 51.90; H, 3.65. (CO) (CH2Cl2) 1939 (s), 1767(w), 1732(vs). 31P{1H} NMR (CDCl3) 3.4. 1H NMR (CDCl3)

7.70-7.30 (m, 5H, Ph), 4.76 (s, 5H, Cp), 4.47 (d, JHP = 342, 2H, PH), 4.45 (d, JHP =
1, 5H, Cp). Preparation of [Fe2Cp2(-PCyH)(-CO)(CO)2]BF4 (2a). Solid [FeCp2]BF4 (0.210 g, 0.771 mmol) was slowly added to an stirred dichloromethane solution (20 mL) of compound 1a (0.335 g, 0.758 mmol) at room temperature, and the mixture was further stirred for 10 min to give a red solution. Solvent was then removed in vacuum and the residue was washed with petroleum ether (5 x 10 mL) to give compound 2a as a red microcrystalline solid (0.380 g, 95 %). Anal. Calcd for C19H22BF4Fe2O3P: C, 43.23; H, 4.20. Found: C, 42.92; H, 3.89. (CO) (CH2Cl2) 2019 (vs), 1990(w), 1833(m). 31P{1H} NMR (CDCl3) 223.4. 1H NMR (CDCl3) 8.13 (dd, JHP = 390, JHH = 10, 1H, PH), 5.17 (s, 10H, Cp), 2.25-1.15 (m, 11H, Cy). Preparation of [Fe2Cp2(-PPhH)(-CO)(CO)2]BF4 (2b). The procedure is completely analogous to that described for 2a. By starting from 0.536g (1.229 mmol) of compound 1b and using 0.335g of [FeCp2]BF4 (1.229 mmol), compound 2b was obtained as a red microcrystalline solid (0.584 g, 91 %). Anal. Calcd for C19H16BF4Fe2O3P: C, 43.73; H, 3.09. Found: C, 43.45; H, 3.15. (CO) (CH2Cl2) 2020 (vs), 1995(w), 1833(m). 31P{1H} NMR (CD2Cl2) 189.6. 1H NMR (CD2Cl2) 9.10 (d, JHP = 413, 1H, PH), 7.80-7.40 (m, 5H, Ph), 5.25 (s, 10H, Cp). Preparation of [Fe2Cp2(-PCy)(-CO)(CO)2] (3a). Solid NaOH (ca. 0.1 g, excess), was added to a dichloromethane solution (6 mL) of compound 2a (0.050 g, 0.095 mmol) at room temperature, and the mixture was vigorously stirred for 5 min to give a red-brown solution which was filtered using a cannula. Solvent was then removed in vacuum from the filtrate and the residue was washed with petroleum ether (2 x 5 mL) to give compound 3a as a red-brown, air-sensitive microcrystalline solid 3

(0.039 g, 95 %). Anal. Calcd for C19H21Fe2O3P: C, 51.87; H, 4.81. Found: C, 51.38; H, 4.47. (CO) (CH2Cl2) 1977 (vs), 1940 (w), 1773 (m). 31P{1H} NMR (C6H6) 531.6. 1H NMR (C6H6) 4.24 (s, 10H, Cp), 2.24-1.47 (m, 11H, Cy). Preparation of [Fe2Cp2(-PPh)(-CO)(CO)2] (3b). The procedure is completely analogous to that described for 3a. By starting from 0.050g (0.096 mmol) of compound 2b and using ca 0.1 g of KOH (excess), compound 3b was obtained as a red-brown, airsensitive microcrystalline solid (0.038 g, 90 %). The crystals used in the X-ray study were grown by slow diffusion of layers of diethyl ether and petroleum ether into a concentrated solution of the complex in dichloromethane at 253 K. Anal. Calcd for C19H15Fe2O3P: C, 52.58; H, 3.48. Found: C, 52.13; H, 3.17. (CO) (CH2Cl2) 1988 (vs), 1952 (w), 1783 (m).
31

P{1H} NMR (CD2Cl2) 498.2. 1H NMR (CD2Cl2) 7.60-7.20

(m, 5H, Ph), 4.90 (s, 10H, Cp). Preparation of [Fe2Cp2(-PCyMe)(-CO)(CO)2]I (4a). Methyl iodide (40 L g, 0.643 mmol) was added to a dichloromethane solution (10 mL) of compound 3a (0.022 g, 0.049 mmol), and the mixture was stirred at room temperature for 10 min to give a red solution which was filtered. Solvent was then removed from the filtrate in vacuum and the residue was washed with petroleum ether (2 x 5 mL) to give compound 4a as a red microcrystalline solid which was dried under vacuum (0.025 g, 88 %). Anal. Calcd for C20H24Fe2IO3P: C, 41.27; H, 4.16. Found: C, 41.12; H, 4.05. (CO) (CH2Cl2) 2015 (vs), 1985(w), 1829(m). 31P{1H} NMR (CD2Cl2) 271.2. 1H NMR (CD2Cl2) 5.37 (s, 10H, Cp), 2.93 (d, JHP = 12, 3H, Me). 2.06-0.88 (m, 11H, Cy). Preparation of [Fe2Cp2{-P(O)Cy}(-CO)(CO)2] (5a). Air was admitted into a Schlenk tube containing a dichloromethane solution (10 mL) of compound 3a (0.022 g, 0.049 mmol), and the mixture was stirred at room temperature for 2 min to give a dark red solution. Solvent was then removed in vacuum, the residue was extracted with dichloromethane / petroleum ether (1/1) and the extracts were chromatographed on an alumina column (activity IV, 15 x 2.5 cm) at 285 K. Elution with acetone gave a red fraction yielding, after removal of solvents under vacuum, compound 5a as a red microcrystalline solid (0.018 g, 81 %). Anal. Calcd for C19H21Fe2O4P: C, 50.04; H, 4.64. Found: C, 49.72; H, 4.30. (CO) (CH2Cl2) 1985 (vs), 1951(w), 1788(m). 31P{1H} NMR (CDCl3) 343.8. 1H NMR (CDCl3) 4.87 (s, 10H, Cp), 2.30-1.25 (m, 11H, Cy). Preparation of [Fe2Cp2{-P(S)Cy}(-CO)(CO)2] (5b). Sulphur (0.007 g, 0.218 mmol) was added to a dichloromethane solution (10 mL) of compound 3a (0.022 g,

0.049 mmol), and the mixture was stirred at room temperature for 2 min to give a redbrown solution. Solvent was then removed in vacuum, the residue was extracted with dichloromethane / petroleum ether (2/1) and the extracts were chromatographed on an alumina column (activity IV, 15 x 2.5 cm) at 285 K. Elution with the same solvent mixture gave a red fraction yielding, after removal of solvents in vacuum, compound 5b as a red-brown microcrystalline solid (0.021 g, 91 %). Anal. Calcd for C19H21Fe2O3PS: C, 48.34; H, 4.48. Found: C, 48.16; H, 4.13. (CO) (CH2Cl2) 1989 (vs), 1957(w), 1794(m). 31P{1H} NMR (CDCl3) 345.6. 1H NMR (CDCl3) 4.81 (s, 10H, Cp), 2.441.25 (m, 11H, Cy). 13C{1H} NMR (CDCl3) 267.5 (s, -CO), 210.3 (d, JCP = 14, FeCO), 91.8 (s, Cp), 62.7 [d, JCP = 20, C1(Cy)], 31.3 [d, JCP = 4, C2(Cy)], 26.6 [d, JCP = 13, C3(Cy)], 25.7 [s, C4(Cy)]. Preparation of solutions of [Fe2Cp2{-1:1,1-CyPCH2CH(CO2Me)C(O)}(CO)(CO)] (6). Methyl acrylate (60 L, 0.67 mmol) was added to a dichloroethane solution (10 mL) of compound 3a (0.025 g, 0.057 mmol), and the mixture was stirred at 303 K for 3 h to give a dark-green solution. Solvent was then removed in vacuum to give a dark-green residue shown (by IR and NMR spectroscopy) to contain compound 6 as major species. All attempts to obtain this very air-sensitive product as a pure material resulted in its progressive decomposition. (CO) (CH2Cl2) 1951 (vs), 1785 (s), 1730 (m, CO2Me), 1611 (m, C(O)Fe) cm-1. 31P{1H} NMR (CD2Cl2) 296.5. 1H NMR (CD2Cl2) 4.76, 4.60 (2 x s, 2 x 5H, Cp), 3.69 (s, 3H, OMe), 2.90-1.20 (m, 14H, PCH2CH and Cy). Preparation of [Fe2Cp2{-P(CH2CH2CO2Me)Cy}(-CO)(CO)2]BF4 (4b). A dichloromethane solution (10 mL) of compound 6, prepared in situ from complex 3a (0.025 g, 0.057 mmol) as described above, was treated at room temperature with HBF4OEt2 (8 L of a 54 % solution in Et2O, 0.060 mmol) for 2 min to give a red solution which was filtered. Solvent was then removed from the filtrate in vacuum and the residue was washed with petroleum ether (2 x 5 mL) and then recrystallized from dichloromethane /petroleum ether to give compound 4b as a red microcrystalline solid (0.018 g, 60 %). Anal. Calcd for C23H28BF4Fe2O5P: C, 44.99; H, 4.60. Found: C, 44.55; H, 4.46. (CO) (CH2Cl2) 2015 (vs), 1985 (w), 1830 (m), 1736 (m, CO2Me). 3.40, 3.24 (2 x m, 2 x 2H, PCH2CH2), 2.20-1.10 (m, 11H, Cy).
31

P{1H}

NMR (CD2Cl2) 276.0. 1H NMR (CD2Cl2) 5.27 (s, 10H, Cp), 3.82 (s, 3H, OMe),

Crystallographic Studies
X-ray Structure Determination of Compound 3b. A single crystal of the complex was coated in high-vacuum grease and mounted on a glass fibre. X-ray measurements were made using a Bruker SMART CCD area-detector diffractometer with Mo-K radiation ( = 0.71073 ).3 Intensities were integrated with the software SAINT3 from several series of exposures, each exposure covering 0.3 in , and the total data set being a hemisphere. Absorption corrections were applied, based on multiple and symmetry-equivalent measurements.4 The structure was solved by direct methods and refined by least squares on weighted F2 values for all reflections.5 All non-hydrogen atoms were assigned anisotropic displacement parameters and refined without positional constraints. All hydrogen atoms were constrained to ideal geometries and refined with fixed isotropic displacement parameters. Complex neutral-atom scattering factors were used.6 Crystallographic data and structure refinement details for 3b are given in the CIF file format. X-ray Structure Determination of Compound 5a. The X-ray intensity data for 5a were collected on a Smart-CCD-1000 Bruker diffractometer using graphitemonochromated Mo-K radiation at 120 K. Cell dimensions and orientation matrixes were initially determined from least-squares refinements on reflections measured in three sets of 30 exposures collected in three diferent regions and eventually refined against all reflections. The software SMART3 was used for collecting frames of data, indexing reflections, and determining lattice parameters. The collected frames were then processed for integration by the software SAINT,3 and a multi-scan absorption correction was applied with SADABS.4 The structure was solved by Patterson interpretation and phase expansion, and was refined by full-matrix least squares on F2 using SHELXL97.7 All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were located in the Fourier map in the last least-squares refinements and were given an overall isotropic thermal parameter. Crystallographic data and structure refinement details for 5a are given in the CIF file format.

References
(1) (2) Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877. Labinger, J. A.; Madhaven, S. J. Organomet. Chem. 1977, 134, 381.

(3) (4) (5) (6) (7)

SMART & SAINT Software Reference Manuals, Version 5.051 (Windows NT Version); Bruker Analytical X-ray Instruments: Madison WI, 1998. Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction; University of Gttingen, Gttingen, Germany, 1996. SHELXTL program system version 5.1; Bruker Analytical X-ray Instruments Inc., Madison, WI, 1998. International Tables for Crystallography, Kluwer, Dordrecht, 1992, vol. C. Sheldrick, G. M. SHELXL97: Program for the Refinement of Crystal Structures; University of Gttingen, Gttingen, Germany, 1997.