| SYNTHESIS |
Abstract: The first dinuclear complex bridged by a substituent-free gallium atom, Cp*Fe(dppe)(-Ga)Fe(CO)4 (1; Cp* = -C5Me5, dppe = Ph2PCH2CH2PPh2), was synthesized by the reaction of Cp*Fe(dppe)GaCl2 with K2[Fe(CO)4]. A crystal structure analysis of complex 1 revealed that the geometry around the gallium atom is essentially linear and the Fe-Ga bonds are significantly shorter than that of usual single bonds. These structural features indicate that the Fe-Ga bonds bear significantly unsaturated character. -------------------------------------------------------------------------------- Transition-metal complexes with metal-gallium unsaturated bonding have excited much recent interest from a structure/bonding viewpoint.1,2 Isolation of the first terminal gallyleneiron complex, (OC)4FeGaAr* (2; Ar* = 2,6-(2,4,6-PriC6H2)2C6H3), by Robinson et al. triggered an extensive discussion.2a A recent theoretical study suggests that the M-ER (M = metal, E = group 13 element) bond in transition-metal complexes with terminal group 13 diyl ligands is mainly ionic but is significantly affected by the -back-donation from the metal to the ER group.3 However, systematic studies to clarify the effect of -bonding have been hampered by the paucity of complexes containing a metal-gallium unsaturated bond.2 Herein we report the synthesis of the first dinuclear complex bridged by a substituent-free gallium atom, [Cp*(dppe)Fe-Ga-Fe(CO)4] (1). The bonding in complex 1 can be depicted as Cp*(dppe)Fe-Ga=Fe(CO)4: i.e., a single bond between Cp*(dppe)Fe and Ga and a double bond between Ga and Fe(CO)4 on the basis of the 18-electron rule. In contrast to expectations, a structural determination revealed that the former is even shorter than the latter, which is attributable to the contribution of strong -back-donation in the former bond. To synthesize the complex in question, we initially examined the salt elimination reaction between the (dichlorogallyl)iron complex Cp*(OC)2FeGaCl2 (3)4 and K2[Fe(CO)4] (4) in THF, which afforded an extremely unstable orange solid of complex 5 (eq 1).5 The product is soluble in THF but insoluble in nonpolar solvents such as benzene and toluene, indicating the ionic nature of complex 5. The 13C NMR spectrum shows two CO signals at 217.2 and 220.5 ppm. The IR spectrum gives six CO bands in the range of 1890-1994 cm-1, whose positions are comparable to those of 3 (1930 and 1981 cm-1), the gallyleneiron complex 2 (1929-2032 cm-1),2a the Cp*Ga complex (OC)4FeGaCp* (6; 1942-2037 cm-1),6 and base-stabilized gallyleneiron complexes (OC)4FeGaR(L2) (R = halogen, alkyl, L = Lewis donor; 1870-2010 cm-1).7 Thus, complex 5 was tentatively assigned to K[{Cp*(OC)2Fe}(-GaCl){Fe(CO)4}]. -------------------------------------------------------------------------------- -------------------------------------------------------------------------------- The structure of 5 was further supported by the fact that addition of bpy (2,2'-bipyridine) to an acetonitrile solution of 5 caused KCl elimination to give a diiron complex bridged by a base-stabilized gallium atom, [Cp*(OC)2Fe](-Ga·bpy)[Fe(CO)4] (7), in 43% yield (eq 2).8 Base-stabilized complexes related to this have been previously reported by us.9 An X-ray crystal structure analysis of 7 (Figure 1) revealed that the gallium atom adopts a distorted-tetrahedral geometry with an Fe(1)-Ga-Fe(2) angle of 136.676(19).10 The Fe(1)-Ga bond length (2.4026(5) Å) is much longer than the corresponding bond lengths of 2 (2.2248(7) Å) and 6 (2.2731(4) Å) and is within the range of those of the base-stabilized gallyleneiron complexes (OC)4Fe-GaR(L2) (2.32-2.42 Å).7 The Fe(2)-Ga bond (2.4221(5) Å) is also within the range of usual Fe-Ga single bonds (2.36-2.46 Å).1b These structural features indicate that the unsaturated bonding character between the iron and gallium atoms is negligible. -------------------------------------------------------------------------------- Figure 1 ORTEP drawing of 7 (thermal ellipsoids at the 50% probability level). Hydrogen atoms are omitted for clarity. Selected interatomic distances (Å) and angles (deg): Ga-Fe(1) = 2.4026(5), Ga-Fe(2) = 2.4221(5), Ga-N(1) = 2.121(2), Ga-N(2) = 2.128(2), Fe(1)-C(1) = 1.766(4), Fe(1)-C(2) = 1.774(4), Fe(1)-C(3) = 1.757(3), Fe(1)-C(4) = 1.765(3); Fe(1)-Ga-Fe(2) = 136.676(19), N(1)-Ga-N(2) = 76.05(10). -------------------------------------------------------------------------------- Attempts to remove chloride from the gallium atom in complex 5 without coordination of bases always led to decomposition. This suggests that it is essential to stabilize the complex electronically by increasing back-donation from the metal center to the unsaturated gallium atom using electron-rich metal fragments. It seems to be also essential to protect sterically the two-coordinate gallium center with bulky metal fragments. Indeed, reaction of the dppe-substituted (dichlorogallyl)iron complex Cp*Fe(dppe)GaCl2 (8) with K2[Fe(CO)4] (4) in THF afforded the first dinuclear complex bridged by a substituent-free gallium atom, Cp*Fe(dppe)(-Ga)Fe(CO)4 (1), where dppe denotes bis(diphenylphosphino)ethane (eq 3).11 Among group 13 elements, only dinuclear complexes containing substituent-free thallium atom have been reported.12 Complex 1 was isolated as orange crystals in 77% yield and fully characterized by NMR, IR, and mass spectroscopy, elemental analysis, and crystal structure analysis. -------------------------------------------------------------------------------- -------------------------------------------------------------------------------- An X-ray crystal structure analysis of 1 revealed that the two-coordinate gallium atom is effectively covered by two phenyl groups of the dppe ligand and the Cp* ligand on Fe(2) (Figure 2).13 The geometry around the gallium atom is essentially linear (176.01(4)), indicating sp hybridization of the gallium atom. The Fe(2)-Ga bond (2.2479(10) Å) is markedly shorter than those of complex 7 and usual Fe-Ga single bonds (2.36-2.46 Å).1b The Fe(1)-Ga bond (2.2931(10) Å) is also significantly shorter than the corresponding bonds of the base-stabilized gallyleneiron complexes (2.32-2.42 Å)7 and slightly longer than those of the terminal gallyleneiron complex 2 (2.2248(7) Å)2a and the Cp*Ga iron complex 6 (2.2731(4) Å).6 These structural features indicate that both Fe-Ga bonds in 1 bear significantly unsaturated character. -------------------------------------------------------------------------------- Figure 2 ORTEP drawing of 1 (thermal ellipsoids at the 50% probability level). Hydrogen atoms are omitted for clarity. Selected interatomic distances (Å) and angles (deg): Ga-Fe(1) = 2.2931(10), Ga-Fe(2) = 2.2479(10), Fe(1)-C(1) = 1.792(6), Fe(1)-C(2) = 1.783(8), Fe(1)-C(3) = 1.769(7), Fe(1)-C(4) = 1.769(7); Fe(1)-Ga-Fe(2) = 176.01(4). -------------------------------------------------------------------------------- According to the 18-electron rule, 1 can be depicted as A in Scheme 1. However, the Fe(2)-Ga bond is shorter than the usual single bond and, surprisingly, even shorter than the Fe(1)-Ga bond. Thus, contribution of the canonical form B is dominant for complex 1. The remarkable shortening of the Fe(2)-Ga bond is attributable to the strong -basic character of the Cp*(dppe)Fe fragment compared to the Fe(CO)4 fragment. The strong -back-donation from the Cp*(dppe)Fe fragment to the empty p orbitals of the Ga atom competes and, consequently, reduces the back-donation from Fe(CO)4 to the Ga atom. This causes the elongation of the Ga-Fe(CO)4 bond in 1 compared to that of 2 and 6. The increasing order of the Ga-Fe(CO)4 bond distances (2 < 6 < 1) indicates that the -basicity of the substituent on the gallium atom increases in the order Ar* < Cp* < Cp*(CO)2Fe. The strong -donation from the Cp*Fe(CO)2 fragment to the Ga atom also increases the electron density of the Ga atom and increases the -donor ability of the Ga fragment to the Fe(CO)4 fragment. Indeed, the trans influence of the Cp*Fe(dppe)Ga fragment toward the Fe(CO)4 fragment is larger than that of Ar*Ga in 2 and Cp*Ga in 6. The Fe(1)-C(1) bond (1.792(6) Å) trans to the Ga atom in 1 is longer than the corresponding bonds of 2 (1.766(5) Å)2a and 6 (1.781(2) Å).6 These data demonstrate the weak back-donation from Fe(CO)4 fragment to the Ga atom in 1 and support the occurrence of strong back-donation from the Cp*(dppe)Fe fragment to the Ga atom. Our result clearly shows the importance of -back-bonding in the metal-gallium bonding. -------------------------------------------------------------------------------- Scheme 1 -------------------------------------------------------------------------------- Acknowledgment This work was supported by a Grant-in-Aid for Scientific Research on Priority Areas (No. 15036211) and Grants-in-Aid for Scientific Research (No. 13440193 and 15350030) from the Ministry of Education, Culture, Sports, Science and Technology of Japan and a Research Grant from Tokuyama Science Foundation. Supporting Information Available Text giving complete experimental details, including synthesis and characterization data of all new compounds, and tables giving crystal structure data; crystal structure data are also available as CIF files. This material is available free of charge via the Internet at http://pubs.acs.org. * To whom correspondence should be addressed. Tel +81-277-30-1261. Fax: +81-277-30-1263. E-mail: ueno@chem.gunma-u.ac.jp. Gunma University. Tohoku University. The University of the Air. 1. (a) Braunschweig, H. Angew. Chem., Int. Ed. 1998, 37, 1882. (b) Fischer, R. A.; Weiss, J. Angew. Chem., Int. Ed. 1999, 38, 2830. (c) Linti, G.; Schnockel, H. Coord. Chem. Rev. 2000, 206, 285. (d) Braunschweig, H.; Colling, M. Coord. Chem. Rev. 2001, 223, 1. 2. (a) Su, J.; Li, X.-W.; Crittendon, R. C.; Campana, C. F.; Robinson, G. H. Organometallics 1997, 16, 4511.[Full text - ACS] (b) Uhl, W.; Benter, M.; Melle, S.; Saak, W. Organometallics 1999, 18, 3778.[Full text - ACS] 3. Uddin, J.; Boehme, C.; Frenking, G. Organometallics 2000, 19, 571.[Full text - ACS] 4. Ueno, K.; Watanabe, T.; Ogino, H. Appl. Organomet. Chem. 2003, 17, 403. 5. 5: 1H NMR (300 MHz, THF-d8) 1.91 (s, 15H, C5Me5); 13C NMR (75.5 MHz, THF-d8) 10.2 (C5Me5), 94.6 (C5Me5), 217.2 (CO), 220.5 (CO); IR (KBr) CO 1890, 1911, 1928, 1967, 1982, 1994 cm-1. 6. Jutzi, P.; Neumann, B.; Reumann, G.; Stammler, H.-G. Organometallics 1998, 17, 1305.[Full text - ACS] 7. (a) Folsing, H.; Segnitz, O.; Bossek, U.; Merz, K.; Winter, M.; Fischer, R. A. J. Organomet. Chem. 2000, 606, 132. (b) Fischer, R. A.; Schulte, M. M.; Weiss, J.; Zsolnai, L.; Jacobi, A.; Huttner, G.; Frenking, G.; Boehme, C.; Vyboishchikov, S. F. J. Am. Chem. Soc. 1998, 120, 1237.[Full text - ACS] (c) Hardman, N. J.; Wright, R. J.; Phillips, A. D.; Power, P. P. J. Am. Chem. Soc. 2003, 125, 2667.[Medline] (d) Reger, D. L.; Graza, D. G.; Rheingold, A. L.; Yap, G. P. A. Organometallics 1998, 17, 3624.[Full text - ACS] 8. 7: 1H NMR (300 MHz, C6D6) 1.79 (s, 15H, C5Me5), 6.45 (m, 2H, bpy), 6.80 (m, 2H, bpy), 7.04 (m, 2H, bpy), 8.95 (m, 2H, bpy); 13C NMR (75.5 MHz, THF-d8) 10.6 (C5Me5), 96.1 (C5Me5), 123.3, 127.3, 142.1, 147.8, 148.0 (bpy), 220.9 (CO); IR (KBr) CO 1858, 1901, 1951, 1982 cm-1. Anal. Calcd for C26H23Fe2GaN2O6; C, 48.73; H, 3.62; N, 4.37. Found: C, 48.53; H, 3.78; N, 4.33. 9. Ueno, K.; Watanabe, T.; Ogino, H. Organometallics 2000, 19, 5679.[Full text - ACS] 10. Crystallographic data for 7: formula C26H23Fe2GaN2O6, fw = 640.88, monoclinic, space group P21/a, a = 14.8574(6) Å, b = 10.9612(4) Å, c = 17.2178(5) Å, = 107.7229(12), V = 2670.93(16) Å3, Z = 4, calcd = 1.594 g cm-3, = 2.166 mm-1, F(000) = 1296, range 1.24-27.41, 339 variables refined with 5158 independent reflections to final R indices (I > 2(I)) of R1 = 0.0418 and wR2 = 0.1093 with GOF = 1.099. 11. 1: 1H NMR (300 MHz, C6D6) 1.43 (s, 15H, C5Me5), 1.97 (m, 2H, PCH2), 2.39 (m, 2H, PCH2), 6.96-7.19 (m, 12H, PPh), 7.41 (m, 4H, PPh), 7.79 (m, 4H, PPh); 13C NMR (75.5 MHz, THF-d8) 10.7 (C5Me5), 33.0 (PCH2), 86.9 (C5Me5), 128.4, 129.5, 130.3, 130.5, 132.8, 134.1, 139.1, 140.5 (PPh), 218.7 (CO); 31P NMR (121.5 MHz, C6D6) 92.9 ppm (dppe); IR (KBr) CO 1878, 1890, 1923, 1998 cm-1. Anal. Calcd for C40H39Fe2GaO4P2; C, 58.09; H, 4.75. Found: C, 58.28; H, 4.89. 12. (a) Balch, A. L.; Nagle, J. K.; Olmstead, M. M.; Reedy, P. E. J. Am. Chem. Soc. 1987, 109, 4123. (b) Schiemenz, B.; Huttner, G. Angew. Chem., Int. Ed. Engl. 1993, 32, 1772. 13. Crystallographic data for 1: formula C40H39Fe2GaO4P2, fw = 827.07, monoclinic, space group P21/c, a = 17.4600(12) Å, b = 10.3435(7) Å, c = 20.7597(19) Å, = 101.494(3), V = 3674.0(5) Å3, Z = 4, calcd = 1.495 g cm-3, = 1.635 mm-1, F(000) = 1696, range 1.19-27.48, 447 variables refined with 7807 independent reflections to final R indices (I > 2(I)) of R1 = 0.0725 and wR2 = 0.1722, with GOF = 1.166. |
| UPDATE | 10.03 |
| AUTHOR |
Keiji Ueno,* Takahito Watanabe, Hiromi Tobita, and Hiroshi Ogino Department of Chemistry, Faculty of Engineering, Gunma University, Kiryu 376-8515, Japan, Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan, and Miyagi Study Center, The University of the Air, Sendai 980-8577, Japan |
| LITERATURE REF. | Organo-metallics, 22, p. 4375 (2003) |
|
Want more information ? Interested in the hidden information ? Click here and do your request. |