398 Acta Chim. Slov. 2005, 52, 398–403 Scientific Paper Syntheses and Crystal Structures of Anionic Lanthanide Chloride Complexes [(CH3)2NH2][LnCl4(HMPA)2] (Ln = La, Nd) and [(CH3)2NH2]4[LnCl6]Cl (Ln = Nd, Sm, Eu) Saša Petriček Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, P.O. Box 537, SI 1001 Ljubljana, Slovenia. E-mail: sasa.petricek@fkkt.uni-lj.si Received 22-07-2005 Abstract Reactions of lanthanide oxides, hexamethylphosphoramide (HMPA), chlorotrimethylsilane and water in tetrahydrofuran (THF) afforded new complexes [(CH3)2NH2][LnCl4(HMPA)2] (Ln = La (1), Nd (2)) and [(CH3)2NH2]4[LnCl6]Cl (Ln = Nd (3), Sm (4), Eu (5)). Lanthanide oxides react with in situ formed HC1, while the cations [(CH3)2NH2]+ are formed by the hydrolysis of HMPA with the cleavage of P-N bonds. Lhe X-ray crystal structures of the complexes 1-5 are reported. Lhe complexes 1 and 2 are the first known compounds with HMPA coordinated to a lanthanide in an anion. Key words: crystal structure, lanthanide chloride complexes, P-N bond cleavage, anionic complexes Introduction Complexes of lanthanide halides with HMPA were well investigated in the past due to the catalytic activity of lanthanide(II) complexes with HMPA in reduction of organic functional groups. Addition of HMPA to Sml2 accelerates rate of reduction of organic halides by Sml2 and provides increased diastereoselectivities in wide range of reactions.1 The reactivity of species depends upon redox potential and substrate access to the metal center. Determination of crystal structures of lanthanide complexes with HMPA, their stability and possibility of ligand displacement is crucial for a better understanding of these processes.2 Molecules of HMPA and anionic ligands are coordinated to lanthanide ion achieving mononuclear molecules or cations in the known complexes. Crystal structures of the complexes depend upon basicity of anions coordinated to a lanthanide and reaction conditions. Strong coordination bonds formed with chloride or isocyanate ligands favour formation of the molecular complexes [LnCl3(HMPA)3],36 [La(NCS)3(HMPA)4]7 and [CeCl4(HMPA)2].8 Cationic complexes are usually formed with weaker ligands as bromide, iodide or trifluoromethansulfonate (OTf): [LnBr2(HMPA)4]Br0.5H2O (Ln = La, Sm),9 [SmBr2(HMPA)4]BrTHF;10 [SmI2(HMPA)4]I(CHCl3)2,11 [Sm(HMPA)3(H20)4]I3, [Sm(HMPA)2(H20)5]I3 •(HMPA)212 and [Ln(OTf)2(HMPA)4]OTf-CHCl3.13 Reaction conditions have also an important influence on the structure of products. Reactions in the presence of air moisture resulted in cationic complexes even if strong anions as chloride are used: [SmCl(HMPA)2 (H20)4]C12THF and [Yb(HMPA)2(H20)5]Cl3HMPA •H20.5 Medium strong anion, such as bromide, form the molecular complex [SmBr3(HMPA)2(THF)]10 at the appropriate molar ratio of samarium to HMPA. Molecular complexes can be prepared also with weak anions like OTL, if appropriate starting compounds are used. For example, [Sm(OTf)3(HMPA)3(H20)]-C HC13 could be prepared from HMPA and anhydrous Sm(OTf)3.14 There is no evidence of lanthanide complexes with HMPA coordinated to a lanthanide in an anion in the literature despite an extensive research of these systems. Preparation and characterisation of anionic lanthanide chloride complexes [LnCl4(HMPA)2]~ are presented in this article. Isolated anions [LnCl6]3~ are characteristic for many complexes of smaller, heavier lanthanides like [(CH3)2NH2]4[LnCl6]Cl (Ln = Ho, Er, Tm,15 Yb)16 or [(CH3)Py]3[LnCl6] (Ln = Dy,17 Tb),18 while larger, lighter lanthanides tend to form dimers or chains to achieve a coordination number higher than six. For example, six chlorides and two waters are coordinated to each praseodymium in the anions [PrCl4(H20)2]", which Petriček Anionic Lanthanide Chloride Complexes Acta Chim. Slov. 2005, 52, 398–403 399 are connected by chlorine bridges into chains.19 Isolated [LnCL]3~ anions of lighter lanthanides are known in [(C6H5)3PH]3[PrCl6]20 and [Nd(E04)2]4[NdCl6]Cl9 (E04 = tetraethylene glycol).21 A combination of isolated [NdCl6]3~ ions and [NdCl4(H20)2]~ chains bridged by chlorides was observed in [CH3NH3]8[NdCl4(H20)2]2 [NdCl6]Cl3.22 Syntheses and crystal structures of neodymium, samarium or europium compounds isotypic to [(CH3)2NH2]4[LnCl6]Cl (Ln = Ho, Er, Tm,15 Yb)16 are described in this article. Results Syntheses Products 1, 2, 3, 4, 5 and [HOP(N(CH3)2)3]Cl were isolated in the one pot synthesis from Ln203, HMPA (written as OP(N(CH3)2)3 in the reactions), (CH3)3SiCl and water in THE The proposed reactions in the suspension are: 2 (CH3)3SiCl + HzO -> (CH3)3Si-0-Si(CH3)3 + 2 HC1 C1) OP(N(CH3)2)3 + 3 HC1 + 3 HzO -> 3 (CH3)2NH2C1 + H3P04 (2) Ln203 + 6 HC1 + 2 (CH3)2NH2C1 + 4 OP(N(CH3)2)3 -> 2 [(CH3)2NH2][LnCl4(OP(N(CH3)2)3)2] + 3 H20 Ln = La (1), Nd (2) (3) Ln203 + 6 HC1 + 8 (CH3)2NH2C1 -> 2 [(CH3)2NH2]4[LnCl6]Cl + 3 H20 Ln = Nd (3), Srn (4), Eu (5) (4) OP(N(CH3)2)3 + HC1 -> [HOP(N(CH3)2)3]Cl (5) The excess of (CH3)3SiCl guarantees a complete consumption of water and in situ formation of HC1 (Reaction 1). [(CH3)2NH2]+ is a product of P-N bond cleavage in HMPA in a presence of HC1 (Reaction 2), as hydrogen halides are known to cleave P-N bonds in phosphoryl amino derivates.23 Ln203 reacts with HC1 and [(CH3)2NH2]C1 according to the reactions 3 and 4 resulting in the precipitated complexes 1, 2 and in the soluble compounds 3, 4 and 5. The complexes 1 and 2 were recrystallized from THE In the cooled reaction solutions grew big crystals of [HOP(N(CH3)2)3]Cl (Reaction 5), which were filtered off and later at room temperature the compounds 3, 4 and 5 crystallized from these solutions during a slow evaporation. The unit celi determined for a selected crystal of [HOP(N(CH3)2)3]Cl was the same as reported in the literature.24 Molecules of HMPA are involved in three processes in the reaction system: coordination of the molecules to a lanthanide, protonation resulting in [HOP(N(CH3)2)3]+ and hydrolysis. The hydrolysis of HMPA affording dimethylammonium chloride provides free chloride ions contributing to the formation of the ionic complexes 1 and 2 instead of molecular ones. The complexes 1 and 2 are the first known compounds with HMPA coordinated to a lanthanide in an anion. In the products 1 and 2 are four chloride ions coordinated to the lanthanide ion on contrary to three in the molecular complexes [LnCl3(HMPA)3] (Ln = La, Pr, Nd, Sm, Eu, Gd), which were prepared from HMPA and [LnCl3(DME)J6'25 or LnCl3.3 Crystal structures of the compounds 1 and 2 The complexes 1 and 2 (Figure 1) are isomorphous, consisting of cation [(CH3)2NH2]+ and anion [LnCl4(HMPA)2]". Four chlorides and two oxygen atoms from HMPA molecules are octahedraly coordinated to a lanthanum or a neodymium ion in [LnCl4(HMPA)2]". It is interesting that HMPA ligands are in cis configuration on contrary to trans configuration of less bulky THF ligands in similar coordination anions [LnCl4(THF)2] (Ln = Er,26 Dy).27 Figure 1. [(CH3)2NH2]+ and [NdCl4(HMPA)2L ions in the complex 2 with the numbering scheme adopted also in the complex 1. Hydrogen atoms are omitted for clarity. The interatomic distances in 1 and 2 listed in Table 1 vary as expected for the lanthanide contraction from lanthanum to neodymium.28 Petriček Anionic Lanthanide Chloride Complexes 400 Acta Chim. Slov. 2005, 52, 398–403 Table 1. Selected bond distances (A) and interatomic angles (°) in the complexes 1 and 2. bond La-l Nd-2 Ln - Cll 2.779(2) 2.715(2) Ln - C12 2.814(1) 2.755(1) Ln - Cl aver. 2.79(2) 2.73(2) Ln-Ol 2.351(4) 2.300(5) Pl-Ol 1.498(5) 1.493(5) Pl-Nll 1.624(4) 1.628(5) P1-N12 1.631(4) 1.629(5) P1-N13 1.641(4) 1.641(5) angle Cll - Ln - C12 91.82(4) 91.89(5) Cll -Ln-Ol 90.1(1) 89.9(1) Cll-Ln-Cll a Cll-Ln-01~a C12-Ln-Or 92.29(5) 177.4(2) 90.1(1) 92.15(6) 177.7(1) 89.7(1) C12-Ln-C12 a C12-Ln-Ol"a Ol-Ln-Olja 176.09(5) 87.0(1) 87.5(2) 175.55(6) 87.1(1) 88.1(2) The average Ln-Cl distances in the anions of 1, 2 are longer than expected according to Pr-Cl distances in the molecular raer-[PrCl3(HMPA)3] (2.72(1) A),3 if only ionic radii of the lanthanides are considered. The observed increase in Ln-Cl distances in the anionic complexes comparing to the molecular one could be explained by a negative partial charge on the lanthanides. The La-O distance in compound 1 is only slightly shorter than in the anion of [LaBr2(HMPA)4] (2.364(4)-2.380(4) A).9 Anions [LnCl4(HMPA)2]~ and dimethylammonium cations are connected into chains by C11...H-N1 and C12...H-N1 hydrogen bonds. Crystal structures of the compounds 3, 4 and 5 The X-ray crystal structures of the compounds 3, 4 and 5 confirm the presence of [(CH3)2NH2]+, [LnCl6]3~ (Ln = Nd, Sm, Eu) and CL ions, similar as in compounds [(CH3)2NH2]4[MC16]C1 reported in the literature for some trivalent transition metals (M = Cr, Rh,29 Mo)30 and some heavier lanthanides (M = Ho, Er, Lm).15 Six chlorides are coordinated to a neodymium, samarium or europium ion in these compounds in a form of slighth/ distorted octahedron as shown by Cl-Ln-Cl angles in Lable 2. Table 2. Selected bond distances (A) and interatomic angles (°) in the complexes 3, 4 and 5. bond Nd-3 Sm-4 Eu-5 Ln - Cll 2.7157(4) 2.6888(6) 2.6756(4) Ln - C12 2.7229(4) 2.6922(7) 2.6799(5) Ln - C13 2.7067(5) 2.6806(8) 2.6681(6) angle Cl - Ln - Cl min. 83.35(2) 84.12(2) 84.24(2) Cl-Ln-Clmax.* 101.56(1) 100.76(2) 100.19(2) Nd-Cl interatomic distances in the complex 3 (Lable 2) are in the same range as the shortest Nd-Cl distances in the complex 2 (Lable 1). Lhe longer distance from neodymium to the chloride C12 in the complex 2 reflect the greater bulkiness of HMPA in comparison to chlorides.31 Similar Nd-Cl interatomic distances as in 3 are reported for [NdCl6]3~ ions in [CH3NH3L[NdCl4(H20)2]2[NdCl6]Cl3 (2.706(2)-2.716(2) A)22 and [Nd(E04)2]4[NdCl6]Cl9 (2.73(1) A).21 Ln-Cl bond distances in 4 (Lable 2) are similar as in /ao[SmCl3(HMPA)3] (2.657(8)-2.680(7) A)6 and in 5 in the same range as in [HPy]2[EuCl5Py] (2.650(2)-2.672(2) A),33 while longer average Ln-Cl distances were reported for anions [LnCl6]3~ in [2,4,6-Lrimethylpyridinium]3[LnCl6] (Sm-Cl 2.759 and Eu-Cl 2.693 A).32 Hydrogen bonds in the complexes 3, 4 and 5 are shown in Pigure 2, while distances betvveen nitrogen and chlorides participating in these bonds are listed in Lable 3. Hydrogen atoms bonded to NI are involved in Nl-H.. .Cll and Nl-H.. .C12 hydrogen bonds connecting [LnCl6]3~ octahedrons and [(CH3)2NH2]+ to anionic layers [(CH3)2NH2]2[LnCl6]". Hydrogen atoms bonded to N2 are involved in N2-H...C14 hydrogen bonds connecting isolated chloride C14 and [(CH3)2NH2]+ to [(CH3)2NH2]2C1+ units, which are betvveen the anionic layers. Figure 2. Hydrogen bonds in the complexes 3, 4 and 5. The same numbering scheme is adopted in ali complexes. Table 3. Distances (A) between nitrogen and chlorides participating in hydrogen bonds in the compounds of 3, 4 and 5. Ln=Nd Ln = Sm Ln = Eu * The maximal interatomic angle involving two neighbouring chlorides. NI-H....Cll N1-H....C12 N1-H....C12 N2-H....C14 3.267(2) 3.291(2) 3.342(2) 3.045(2) 3.264(3) 3.288(3) 3.343(3) 3.047(3) 3.263(2) 3.288(2) 3.343(2) 3.047(2) Petriček Anionic Lanthanide Chloride Complexes Acta Chim. Slov. 2005, 52, 398–403 401 Conclusions The reactions in the suspension of lanthanide oxides in THF, HMPA, trichlorotrimethylsilane and water afforded new anionic complexes of lanthanide chlorides. HC1 formed in situ from trichlorotrimethylsilane and water causes a cleavage of P-N bonds in HMPA and the formation of [(CH3)2NH2]C1. The suspended lanthanide oxides react with hydrogen chloride, resulted predominately in precipitated [(CH3)2NH2] [LnCl4(HMPA)2] and partly in soluble [LnCL]3-. In the HMPA complexes obtained in investigated systems four chloride ions and two molecules of HMPA are coordinated to the central lanthanide ion instead of only three chlorides in molecular [LnCl3(HMPA)3]. The molecular complexes [LnCl3(HMPA)3] were prepared from anhydrous lanthanide chlorides3 or [LnCl3(DME)2]6 by addition of HMPA to the solvent. The formation of anionic complexes [LnCl4(HMPA)2]~ could be explained by an excess of free chloride ions provided by the hydrolysis of HMPA which resulted in dimethylammonium chloride. Isolated anions [LnCl6]3~ of lighter lanthanides were crystallized as [(CH3)2NH2]4[LnCl6]Cl (Ln = Nd, Sm, Eu), which are isotypic to the compounds of some heavier lanthanides (Ln = Ho, Er, Tm 15 and Yb).16 Experimental General Ali the manipulations were carried out under an atmosphere of purified argon. Lanthanide oxides (Aldrich, 99.99%), chlorotrimethylsilane (Aldrich, 97%), HMPA (Aldrich, 99%) were used as received, THF was dried over Na/K alloy. The solvents were distilled before use. The suspensions of ground samples in nujol were prepared in a dry box. IR spectra were recorded on a Perkin Elmer 1720X instrument betvveen 400 and 4000 cm4. The lanthanide content was determined by a gravimetric analysis. The complexes were dissolved, precipitated as oxalates, which decompose at higher temperatures to lanthanide oxides. Elemental analyses were obtained by a Perkin-Elmer 2400 CHN analyser at University of Ljubljana (Department of Organic Chemistry). The JH NMR spectra were recorded on a Bruker DPX 300 spectrometer. Syntheses [(CHJ^HJ[LaCl4(HMPA)J - 1 30 mL of THF, 1.97 g (11.0 mmol) of HMPA, 13.99 g (129 mmol) of (CH3)3SiCl and 0.090 g (5.0 mmol) of water were added to 0.330 g (1.01 mmol) of La203. The suspension was stirred for one day, the solution was decanted and the solid residual dried in vacuo. 1.11 g (80% yield) of the complex 1 was gained. Anal. Calcd for C14H44Cl4N7La02P2: H 6.47, C 24.54, N 14.31, La 20.3. Found: H 6.42, C 24.32, N 14.20, La 20.1. IR (Nujol): 1298 s, 1186 m, 1143 m, 1119 s, 1071 w, 987 vs, 874 w, 802 w, 758 s, 482 m cm4. JH NMR, (300 MHz, CDC13) 8 9.00 (s, 2H, (CH3)2Nff2+), 2.79 (t, 6H, (C//3)2NH2+), 2.72, J(PH) 9 Hz (d, 36H, HMPA). Colourless crystals of the complex 1 grew out of the THF solution during a slow evaporation of the solvent. [(CHJ^HJ[NdCl4(HMPA)2] - 2 25 mL of THF, 1.07 g (5.98 mmol) of HMPA, 12.17 g (112 mmol) of (CH3)3SiCl and 0.090 g (5.0 mmol) of water were added to 0.340 g (1.01 mmol) of Nd203. The suspension was stirred for one day, the solution was decanted and the solid residual dried in vacuo 1.13 g (81% yield) of the complex 2 was gained. Anal. Calcd For C14H44Cl4N7Nd02P2: H 6.42, C 24.35, N 14.20, Nd 20.9. Found: H 6.23, C 24.22, N 14.00, Nd 21.0. IR (Nujol): 1301 s, 1191 s, 1167 m, 1123 vs, 1065 m, 1013 s, 987 vs, 870 w, 802 w, 753 m, 613 w, 483 m, 454 w cm4. Bright, pale blue crystals grew out of the THF solution during a slow evaporation of the solvent. [(CHJ^HJ'4[NdCl6]Cl - 3 18 mL of THF, 2.29 g (12.8 mmol) of HMPA, 12.34 g (114 mmol) of (CH3)3SiCl and 0.090 g (5.0 mmol) of water were added to 0.340 g (1.01 mmol) of Nd203. The suspension was stirred for one day, then the blue solution was filtered off. A lot of white crystals of [HOP(N(CH3)2]Cl grew out of the solution at 4 °C, but the solution was stili coloured. The blue solution was separated from the white crystals. Pale blue crystals of the complex 3 (yield less than 10%) grew during a slow evaporation of the solution at room temperature. Anal. Calcd for C8H32CLN4Nd: H 5.59, C 16.66, N 9.71. Found: H 5.51, C 16.61, N 9.72. IR (Nujol): 3166 m, 1569 w, 1154 w, 1013 m, 888 w, 836 w, 810 w cm4. [(CHJ^HJ'4[SmCl6]Cl - 4 30 mL of THF, 1.17 g (6.53 mmol) of HMPA, 14.07 g (130 mmol) of (CH3)3SiCl and 0.120 g (6.67 mmol) of water were added to 0.440 g (1.26 mmol) of Sm203. The suspension was stirred for one day, then the solution was filtered off. A lot of large white crystals of [HOP(N(CH3)2]Cl grew out of the solution at 4 °C. After removal of the white crystals of [HOP(N(CH3)2]Cl colourless crystals of the complex 4 (yield less than 10%) grew during a slow evaporation of the solution at room temperature. Anal. Calcd for C8H32CLN4Sm: H 5.53, C 16.48, N 9.61. Found: H 5.36, C 16.69, N 9.47. IR (Nujol): 3160 w, 1570 w, 1028 m, 889 w, 810 w cm4. Petriček Anionic Lanthanide Chloride Complexes 402 Acta Chim. Slov. 2005, 52, 398–403 [(CH^^HJ'4[EuCl6]Cl - 5 35 mL of THF, 0.988 g (5.51 mmol) of HMPA, 11.63 g (107 mmol) of (CH3)3SiCl and 0.080 g (4.44 mmol) of water were added to 0.310 g (0.88 mmol) of Eu203. The suspension was stirred for one day, then the solution was filtered off. A lot of large white crystals of [HOP(N(CH3)2]Cl grew out of the solution at 4 °C. After removal of the white crystals of [HOP(N(CH3)2]Cl colourless crystals of the complex 5 (yield less than 10%) grew during a slow evaporation of the solution at room temperature. Anal. Calcd for C8H32CLEuN4: H 5.52, C 16.44, N 9.59. Found: H 5.46, C 16.40, N 9.41. Crystal structure determination The details of the crystal data collections and refinement parameters are listed in Table 4 (compounds 1, 2) and Table 5 (compounds 3, 4, 5). Ali studied compounds were hygroscopic. The crystals were greased on a glass thread. Diffraction data were collected on a Nonius Kappa CCD diffractometer with a CCD area detector at 150(2) K. A graphite monochromatic Mo Ka radiation (X = 0.71073 A) was employed in ali measurements. The structures were solved by direct methods implemented in SHELXS-9734 and refined by a full-matrix least-squares procedure based on F2 (SHELXL-97)35 included to WinGX vi.70.01.36 Ali non-hydrogen atoms were refined anisotropically, while aH the hydrogen atoms in compounds 2, 3, 4 and 5 were included in the model at geometricalfy calculated positions and refined using a riding model. Only the two hydrogen atoms bonded to nitrogen in [NH2(CH3)2] + in the compound 1 were located from a AF synthesis and included in the refinement at calculated positions with the isotropic displacement parameters of 1.2 times the U value of the respective nitrogen atom. Nitrogen atoms in [NH2(CH3)2]+ ions of the compounds 1 and 2 are in two disordered positions, each site occupied by a half. The absolute structures were determined for the compounds 3 and 4, while racemic tvvinning (Flack parameter 0.288(6)) was considered in the refinement of the compound 5. Table 4. Crystallographic data, data collection and structure refinement data of the compounds 1 and 2. i 2 Chemical formula Crystal system Space group a, b, c [A] «, p, m F [A3] Z Dcalc [g/cm3] MMoK«) [mm-1] Crystal colour Crystal Size [mm] 6>range [°] Data meas., unique Data used, threshold Numberof parameters TAobserved),^4, S Max./min. res. el. dens.[e/A3] Ci4H,4Cl4N7La02P2 Monoclinic C2/c (No. 15) 17.5692(2) 10.8556(2) 16.1248(2) 90, 98.761(1), 90 3039.51(8) 4 1.497 1.885 colourless 0.18 x 0.14x0.14 3.24, 27.45 6519,3462 3090, [7>2.0o(7)] 0.0179 154 0.0379,0.0832, 1.083 1.14,-1.06 Cl4H44Cl4N7Nd02P2 Monoclinic C2/c (No. 15) 17.5464(5) 10.7820(3) 16.0462(5) 90, 99.105(2), 90 2997.46(15) 4 1.530 2.2 light blue 0.08 x 0.05 x 0.05 3.26, 27.47 6140, 3420 2446, [7 > 2.0 o(/)] 0.0489 152 0.0462, 0.0782, 1.054 0.85, -0.70 a R = (|F01 - |Fo |)/ |F01. b wR2 = ([w(F02 - Fo2)2]/ (wF02)2)1/2. Table 5. Crystallographic data, data collection and structure refinement data of the compounds 3, 4 and 5. ______________________________________________3_______________________4_________________ 5 Chemical formula Crystal System Space group a, b, c [A] v [A3] Z (space group/ formula) Dcak [g/cm3] /range [°] Data meas., used Unique refl. + Fr.rel. Threshold Numberof param. 7?(observed),7?w6 S Flack parameter Max./min.res.el.dens.[e/A3] C8H32Cl7N4Nd Orthorhombic P2,2,2 (No. 18) 8.6883(1) 10.3508(2) 13.3495(2) 1200.53(3) 4/2 1.596 2.9 light blue 0.25 x0.23 x0.17 1.02,27.9 2803, 2785, 1658 + 1145 [7>2.0a(7)] 96 0.0136,0.0330 1.14 0.013(7) 0.33,-0.52 C8H32Cl7N4Sm Orthorhombic P2,2,2(No. 18) 8.6909(1) 10.3378(2) 13.2640(2) 1191.70(3) 4/2 1.624 3.2 colourless 0.1 x0.1 x0.08 1.02,27.5 2741, 2620 1592+1149 [7> 2.0a(7)] 96 0.0218,0.0408 1.06 0.013(10) 0.83,-0.63 C8H32Cl7EuN4 Orthorhombic P2,2,2 (No. 18) 8.6965(1) 10.3204(1) 13.2304(2) 1187.45(3) 4/2 1.635 3.4 colourless 0.11 x0.10 x0.09 1.02,27.5 2731,2682 1587+1144 [7>2.0a(7)] 97 0.0142, 0.0304 1.06 0.288(6) 0.46, -0.46 "R = (\Fg\ - \FC\)I \Fg\. b wR2 = ([w(F02 - Fc2)2]/ (wF02)2)"2. Petriček Anionic Lanthanide Chloride Complexes Acta Chim. Slov. 2005, 52, 398–403 403 Supplementary material CCDC 278818 (1), CCDC 278817 (2), CCDC 278814 (3), CCDC 278815 (4) and CCDC 278816 (5) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. Acknowledgements The Ministry of Education, Science and Šport, Republic of Slovenia supported this work, through grants MŠZŠ Pl-0175 and X-2000. A special thank is given to Prof. Alojz Demšar for helpful discussions. References 1. A. Molander, Chem. Rev. 1996, 96, 307-338. 2. E. Prasad, B. W. Knettle, R. A. Flovvers, /. Am. Chem. Soc. 2004, 126, 6891-6894. 3. L. J. Radonovich, M. D. Glick,/. Inorg. Nucl. Chem. 1973, 35, 2745-2752. 4. X. W. Zhang, X. F. Li, F. Benetollo, G. Bombieri, Inorg. Chim. Acta 1987, 139, 103-104. 5. Z. Hou, K. Kobayashi, H. Yamazaki, Chem. Lett. 1991, 268, 265-268. 6. S. Petriček, A. Demšar, L. Golič, J. Košmrlj, Polyhedron 2000, 19, 199-204. 7. D. Barr, A. T. Brooker, M. J. Doyle, S. R. Drake, P. R. Raithby, R. Snaith, D. S. Wright, Angew. Chem. 1990, 102, 300-301. 8. J. G. H. du Preez, H. E. Rohwer, J. F. de Wet, M. R. Caira, Inorg. Chim. Acta 1978, 26, 59-60. 9. S. Petriček, Z. Anorg. Allg. Chem. 2005, 631, 1947-1952. 10. K. Asakura, T. Imamoto, Buli. Chem. Soc. Jpn. 2001, 74, 731-732. 11. A.Cabrera, M. Salmon, N. Rosas, J. Perez-Flores, L. Velasco, G. Espinoza-Perez, J. L. Arias, Polyhedron 1998, 17, 193-197. 12. T. Imamoto, Y. Yamanoi, H. Tsuruta, K. Yamaguchi, M. Yamazaki, J. Inanaga, Chem. Lett. 1995, 949-950. 13. T. Imamoto, M. Nishiura, Y. Yamanoi, H. Tsuruta, K Yamaguchi, Chem. Lett. 1996, 875-876. 14. M. Nishiura, Y. Yamanoi, H. Tsuruta, K. Yamaguchi, T. Imamoto, Buli. Soc. Chim. Fr. 1997, 134, 411-420. 15. A. Becker, W. Urland, /. Alloys Com. 1998, 275-277, 62-66. 16. M. Czjzek, H. Fuess, I. Pabst, Z. Anor. Allg. Chem. 1992, 617, 105-109. 17. J. Hallfeldt, W. Urland, Z. Anor. Allg. Chem. 2001, 627, 545-548. 18. W. Urland, J. Hallfeldt, Z. Anor. Allg. Chem. 2000, 626, 2569-2573. 19. A. Becker, W. Urland, Z. Anor. Allg. Chem. 1999, 625, 1033-1036. 20. R. J. Majeste, D. Chriss, T. M. Trefonas, Inorg. Chem. 1977, 16, 188-191. 21. R. D. Rogers, A. N. Rollins, R. F. Henry, J. S. Murdoch, R. D. Etzenhouser, S. E. Huggins, T. Nunez, Inorg. Chem. 1991, 30, 4946-4954. 22. P. Runge, M. Schulze, W. Urland, Z. Anorg. Allg. Chem. 1991, 592, 115-120. 23. R. H. Neilson, Encyclopedia oflnorganic Chemistry, edited by R. B. King, Wiley, Chichester, UK, 1994, 6, 3183. 24. X. D. Tiu, J. G. Verkade, Inorg. Chem. 1998, 37, 5189-5197. 25. S. Petriček, A. Demšar, T. Golič, Polyhedron 1999, 18, 529-532. 26. S. Anfang, M. Kari, N. Faza, W. Massa, J. Magull, K. Dehnicke, Z. Anorg. Allg. Chem. 1997, 623, 1425-1432. 27. G. R. Willey, P. R. Meehan, T. J. Woodman, M. G. B. Drew, Polyhedron 1997, 16, 623-627. 28. R. D. Shanonn,^4cto Cryst. 1976, A32, 751-767. 29. O. S. Filipenko, D. D. Makitova, O. N. Krasočka, V I. Ponomarev, T. O. Atovmal, Coord. Chimia 1987, 13, 669-672. 30. I. Teban, P. Šegedin, Z. Kristallographie 1993, 206, 69-75. 31. J. Marçalo, A. P. Matos, Polyhedron 1989, 8, 2431-2437. 32. Crystallographic data obtained through the Cambridge Crystallographic Data Centre, [2,4,6-Trimethylpyridiniu m]3[TnCl6], Tn = Sm (refcode: UNEREK), Eu (refcode: UNECAF), J. Hallfeldt, Contribution from the thesis of J. Hallfeldt, University of Hannover, Germany 2003. 33. J. S. 11, B. Neumuller, K Dehnicke, Z. Anorg. Allg. Chem. 2002, 628, 2785-2789. 34. G. M. Sheldrick, SHETXS-97, University of Göttingen, Göttingen, Germany, 1997. 35. G. M. Sheldrick, SHETXT-97, University of Göttingen, Göttingen, Germany, 1997. 36. T. J. Farrugia,/. Appl. Cryst. 1999, 32, 837-838. Povzetek Po reakciji med lantanoidnimi oksidi, heksametilfosforamidom (HMPA), klorotrimetilsilanom in vodo v tetrahidrofuranu (THF) nastanejo novi kompleksi, oborita se [(CH3)2NH2][LnCl4(HMPA)2] (Ln = La (1), Nd (2)), iz raztopine pa izkristalizirajo [(CH3)2NH2]4[LnCl6]Cl (Ln = Nd (3), Sm (4), Eu (5)). Lantanoidni oksidi reagirajo s HCl, ki nastane in situ, kationi [(CH3)2NH2]+ pa nastanejo po hidrolizi HMPA s cepitvijo P–N vezi. Poročamo o kristalnih strukturah spojin 1–5. Kompleksa 1 in 2, sta prvi znani spojini v katerih je ligand HMPA koordiniran v anionu. Petriček Anionic Lanthanide Chloride Complexes