N,N'-diisopropyl-N'-bis(trimethylsilyl)guanidinate ligand as a supporting coordination environment in yttrium chemistry. Synthesis, structure, and properties of complexes [(Me(3)Si)(2)NC(Ni-Pr)(2)]YCl(2)(THF)(2), [(Me(3)Si)(2)NC(Ni-Pr)(2)]Y(CH(2)SiMe(3))(2)(THF)(2), and [(Me(3)Si)(2)NC(Ni-Pr)(2)]Y[(mu-H)(mu-Et)(2)BEt](2)(THF)

The reaction of anhydrous YCl3 with an equimolar amount of lithium N,N'-diisopropyl-N' '-bis(trimethylsilyl)guanidinate, Li[(Me3Si)2NC(Ni-Pr)2], in tetrahydrofuran (THF) afforded the monomeric monoguanidinate dichloro complex {(Me3Si)2NC(Ni-Pr)2}YCl2(THF)2 (1). Alkylation of complex 1 with 2 equiv of LiCH2SiMe3 in hexane at 0 degrees C yielded the monomeric salt-free dialkyl complex {(Me3Si)2NC(Ni-Pr)2}Y(CH2SiMe3)2(THF)2 (2). The bis(triethylborohydride) complex [(Me3Si)2NC(Ni-Pr)2]Y[(mu-H)(mu-Et)2BEt]2(THF) (5) was prepared by the reaction of complex 1 with 2 equiv of LiBEt3H in a toluene-THF mixture at 0 degrees C. The complexes 1, 2, and 5 were structurally characterized. Complex 2 as well as the systems 2-Ph3B, 2-Ph3B-MAO, and 1-MAO (MAO = methylaluminoxanes) in toluene were inactive in ethylene polymerization, while the product obtained in situ from the reaction of complex 2 with a 2-fold molar excess of PhSiH3 in toluene polymerized ethylene with moderate activity.     

Aluminium complexes with thio-phosphorus ligands: syntheses and characterisations of [Al(2)(CyPS(3))(2)(CyPHS(2))(2)] and [Al(S(2)PPh(2))(3)

The novel aluminium complexes [Al(2)(CyPS(3))(2)(CyPHS(2))(2)] and [Al(S(2)PPh(2))(3)] have been prepared as potential models for alumino-thiophosphonate based materials; [Al(2)(CyPS(3))(2)(CyPHS(2))(2)] is the first example of a primary dithiophosphinate to be characterised in the solid state.     

Synthesis, crystal structure, and magnetic studies of oxo-centered trinuclear chromium(III) complexes: [Cr(3)(mu(3)-O)(mu(2)-PhCOO)(6)(H(2)O)(3)]NO(3). 4H(2)O.2CH(3)OH, a case of spin-frustrated system, and [Cr(3)(mu(3)-O)- (mu(2)-PhCOO)(2)(mu(2)-OCH(2)CH(3))(2)(bpy)(2)(NCS )(3)], a new type of [Cr(3)O] core

The synthesis, crystal structure, and magnetic properties of two trinuclear oxo-centered carboxylate complexes are reported and discussed: [Cr3(mu3-O)(mu2-PhCOO)6(H2O)3]NO3.4H2O.2CH3OH (1) and [Cr3(mu3-O)(mu2-PhCOO)2(mu2-OCH2CH3)2(bpy)2(NCS)3] (2). For both complexes the crystal system is monoclinic, with space group C2/c for 1 and P1/n for 2. The structure of complex 1 consists of discrete trinuclear cations, associated NO3- anions, and lattice methanol and water molecules. The structure of complex 2 is built only by neutral discrete trinuclear entities. The most important feature of 2 is the unusual skeleton of the [Cr3O] core due to the lack of peripheral bridging ligands along one side of the triangular core, which is unique among the structurally characterized (mu3-oxo)trichromium(III) complexes. Magnetic measurements were performed in the 2-300 K temperature range. For complex 1, in the high-temperature region (T > 8 K), experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -2J12S1S2 - 2J13S1S3 - 2J23S2S3 (J12 = J13 = J23) with Jij = -10.1 cm(-1), g = 1.97, and TIP = 550 x 10(-6) emu mol(-1). The antisymmetric exchange interaction plays an important role in the magnetic behavior of the system, so in order to fit the experimental magnetic data at low temperature, a new magnetic model was used where this kind of interaction was also considered. The resulting fitting parameters are the following: Gzz = 0.25 cm(-1), delta = 2.5 cm(-1), and TIP = 550 x 10(-6) emu mol(-1). For complex 2, the experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -2J1(S1S2 + S1S3) - 2J2(S2S3) with J1 = -7.44 cm(-1), J2 = -51.98 cm(-1), and g = 1.99. The magnetization data allows us to deduce the ground term of S = 1/2, characteristic of equilateral triangular chromium(III) for complex 1 and S = 3/2 for complex 2, which is confirmed by EPR measurements.     

Oligomerization and oxide formation in bismuth aryl alkoxides: synthesis and characterization of Bi4(mu 4-O)(mu-OC6F5)6(mu 3-OBi(mu-OC6F5)3)2(C6H5CH3), Bi8(mu 4-O)2(mu 3-O)2(mu-OC6F5)16, Bi6(mu 3-O)4(mu 3-OC6F5)(mu 3-OBi(OC6F5)4)3, NaBi4(mu 3-O)2(OC6F5)9(THF)2, and Na2Bi4(mu 3-O)2(OC6F5)10(THF)2

Exposing [Bi(OR)3(toluene)]2 (1, R = OC6F5) to different solvents leads to the formation of larger polymetallic bismuth oxo alkoxides via ether elimination/oligomerization reactions. Three different compounds were obtained depending upon the conditions: Bi4(mu 4-O)(mu-OR)6(mu 3-OBi(mu-OR)3)2(C6H5CH3) (2), Bi8(mu 4-O)2(mu 3-O)2(mu 2-OR)16 (3), Bi6(mu 3-O)4(mu 3-OR)(mu 3-OBi(OR)4)3 (4). Compounds 2 and 3 can also be synthesized via an alcoholysis reaction between BiPh3 and ROH in refluxing dichloromethane or chloroform. Related oxo complexes NaBi4(mu 3-O)2(OR)9(THF)2 (5) and Na2Bi4(mu 3-O)2(OR)10(THF)2 (6) were obtained from BiCl3 and NaOR in THF. The synthesis of 1 and Bi(OC6Cl5)3 via salt elimination was successful when performed in toluene as solvent. For compounds 2-6 the single-crystal X-ray structures were determined. Variable-temperature NMR spectra are reported for 2, 3, and 5.     

Triangular oxalate clusters [W(3)(mu(3)-S)(mu(2)-S(2))(3)(C(2)O(4))(3)](2)(-) as building blocks for coordination polymers and nanosized complexes

The reaction of aqueous [W3S7(C2O4)3](2-) with Ln(3+) and Th(4+) in a 1:1 molar ratio leads to oxalate-bridged heteropolynuclear molecular complexes and coordination polymers. La(3+) and Ce(3+) give a layered structure with big (about 1.8 nm) honeycomb pores which are filled with water molecules and lanthanide ions, in {[Ln(H2O)6]3[W3S7(C2O4)3]4}Br x xH2O (Ia and Ib). The smaller Pr(3+), Nd(3+), Sm(3+), Eu(3+), and Gd(3+) ions give discrete nanomolecules [(W3S7(C2O4)3Ln(H2O)5)2(mu-C2O4)] (with a separation of about 3.2 nm between the most distant parts of the molecule), which are further united into zigzag chains by specific S2...Br- contacts to achieve the overall stoichiometry K[(W3S7(C2O4)3Ln(H2O)5)2(mu-C2O4)]Br.xH2O (IIa-IId). Th(4+) gives K2[(W3S7(C2O4)3)4Th2(OH)2(H2O)10] x 14.33H2O (III) with a nanosized discrete anion (with a separation of about 2.7 nm between the most distant parts of the molecule), in which two thorium atoms are bound via two hydroxide groups into the Th2(OH)2(6+) unit, and each Th is further coordinated by five water molecules and two monodentate [W3S7(C2O4)](2-) cluster ligands. All compounds were characterized by X-ray structure analysis and IR spectroscopy. Magnetic susceptibility measurements in the temperature range of 2-300 K show weak antiferromagnetic interactions between two lanthanides atoms for compounds IIa, IIb, and IId. The thermal decomposition of Ia, Ib, and IIb was studied by thermogravimetry.     

On the road to a termolecular complex with acetone: a heterometallic supramolecular network [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]

A novel heterometallic supramolecular network [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]](2)( infinity ) has been prepared by codeposition of the volatile mono(acetone) adduct [Rh(2)(O(2)CCF(3))(4).eta(1)-OCMe(2)](2) and copper(I) trifluoroacetate, [Cu(4)(O(2)CCF(3))(4)]. The product is of interest from the viewpoints of gas-phase supramolecular synthesis and a rare bridging coordination mode of acetone. It has been fully characterized by IR and NMR spectroscopy, elemental analysis, and X-ray diffraction. An X-ray structure revealed a layered 2D arrangement of the heterometallic [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]] units built by axial intermolecular interactions of the open electrophilic Rh(II) and Cu(I) centers and O-atoms of neighboring carboxylate groups. The coordination of the acetone molecules within the [[Rh(2)(O(2)CCF(3))(4)].micro(2)-OCMe(2).[Cu(4)(O(2)CCF(3))(4)]] unit is asymmetric with the Rh-O and Cu-O distances being 2.2173(15) and 2.7197(17) A, respectively. This work shows the potential of gas-phase deposition that may provide additional possibilities in supramolecular synthesis by utilizing intermolecular interactions and coordination bonds in a new way compared with conventional solution chemistry.     

Cation ordering in natural and synthetic (Cu(1-x)Zn(x))(2)CO(3)(OH)(2) and (Cu(1-x)Zn(x))(5)(CO(3))(2)(OH)(6)

In the present paper we report combined experimental and theoretical studies of the UV-vis-NIR spectra of the mineral compounds malachite, rosasite, and aurichalcite and of the precursor compounds for Cu/ZnO catalysts. For the copper species in the minerals the crystal field splitting and the vibronic coupling constants are estimated using the exchange charge model of the crystal field accounting for the exchange and covalence effects. On this basis the transitions responsible for the formation of the optical bands arising from the copper centers in minerals are determined and the profiles of the absorption bands corresponding to these centers are calculated. The profiles of the absorption bands calculated as a sum of bands of their respective Cu species are in quite good agreement with the experimental data. In agreement with crystal chemical considerations, the Zn ions were found to be preferentially located on the more regular, i.e., less distorted, octahedral sites in zincian malachite and rosasite, suggesting a high degree of metal ordering in these phases. This concept also applies for the mineral aurichalcite, but not for synthetic aurichalcite, which seems to exhibit a lower degree of metal ordering. The catalyst precursor was found to be a mixture of zincian malachite and a minor amount of aurichalcite. The best fit of the optical spectrum is obtained assuming a mixture of contributions from malachite (0% Zn) and rosasite (38% Zn of [Zn + Cu]), which is probably due to the intermediate Zn content of the precursor (30%).     

Further evidence for the tetraoxoiodate(V) anion,IO(4)(3-): hydrothermal syntheses and structures of Ba[(MoO(2))(6)(IO(4))(2)O(4)] x H(2)O and Ba(3)[(MoO(2))(2)(IO(6))(2)] x 2H(2)O

The hydrothermal reaction of MoO(3) with BaH(3)IO(6) at 180 degrees C for 3 days results in the formation of Ba[(MoO(2))(6)(IO(4))(2)O(4)] x H(2)O (1). Under similar conditions, the reaction of Ba(OH)(2) x 8H(2)O with MoO(3) and Ba(IO(4))(2) x 6H(2)O yields Ba(3)[(MoO(2))(2)(IO(6))(2)] x 2H(2)O (2). The structure of 1, determined by single-crystal X-ray diffraction, consists of corner- and edge-sharing distorted MoO(6) octahedra that create two-dimensional slabs. Contained within this molybdenum oxide framework are approximately C(2v) tetraoxoiodate(V) anions, IO(4)(3-), that are involved in bonding with five Mo(VI) centers. The two equatorial oxygen atoms of the IO(4)(3-) anion chelate a single Mo(VI) center, whereas the axial atoms are mu(3)-oxo groups and complete the octahedra of four MoO(6) units. The coordination of the tetraoxoiodate(V) anion to these five highly electropositive centers is probably responsible for stabilizing the substantial anionic charge of this anion. The Ba(2+) cations separate the layers from one another and form long ionic contacts with neighboring oxygen atoms and a water molecule. Compound 2 also contains distorted MoO(6) octahedra. However, these solely edge-share with octahedral hexaoxoiodate(VII), IO(6)(5-), anions to form zigzagging one-dimensional, (1)(infinity)[(MoO(2))(IO(6))](3-), chains that are polar. These chains are separated from one another by Ba(2+) cations that are coordinated by additional water molecules. Bond valence sums for the iodine atoms in 1 and 2 are 5.01 and 7.03, respectively. Crystallographic data: 1, monoclinic, space group C2/c, a = 13.584(1) A, b = 7.3977(7) A, c = 20.736(2) A, beta = 108.244(2) degrees, Z = 4; 2, orthorhombic, space group Fdd2, a = 13.356(7) A, b = 45.54(2) A, c = 4.867(3) A, Z = 8.     

Structural characterization of the first hydroxo-bridged plutonium compound, (PuO(2))(2)(IO(3))(mu(2)-OH)(3)

The hydrothermal reaction of a (239)Pu(IV) stock solution in the presence of iodic acid and 1 M KOH produces reddish-brown single crystals of (PuO(2))(2)(IO(3))(OH)(3). The structure consists of two-dimensional layers forming in the ac plane and is the first single-crystal structure of plutonium(VI) connected through hydroxide anions. The additional linkage of plutonium centers is completed through iodate ligands.     

A mechanistic study of the samarium(II)-mediated reduction of aryl nitro compounds to the corresponding crylamines. The crystal structures of [Sm[N(SiMe(3))(2)](2)(thf)](2)(mu(2)-O) and [(Me(3)Si)(2)N](2)Sm(thf)(mu-PhNNPh)Sm[N(SiMe(3))(2)](2)

Treatment of nitrobenzene and other various nitroarenes with 6 equiv of samarium(II) under strictly anhydrous conditions allows for the isolation of aniline or the corresponding arylamine. Reducing the number of samarium(II) equivalents allows for the isolation of intermediate species, e.g., azoarenes or hydrazines. Use of Sm[N(SiMe(3))(2)](2), in place of the typically used SmI(2), has allowed for the detailed examination of the aqueous and nonaqueous species formed in this reduction and has been instrumental in delineation of the stepwise reaction mechanism. This is the first time that the reaction intermediates of an organic reaction mediated by samarium(II) have been isolated and analyzed by (1)H NMR and X-ray crystallography.     

Synthesen und Kristallstrukturanalysen von [SbI3(SbMe3)(THF)]2 und [Li(THF)4]2[Bi2Cl8(THF)2]

Syntheses and Crystal Structure Analyses of [SbI₃(SbMe₃)(THF)]₂ and [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] The reaction of Me₃Sb with SbI₃ in tetrahydrofuran (THF) gives [SbI₃(SbMe₃)(THF)]₂ ( 1 ). [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] ( 2 ) is formed by reaction of LiCl and BiCl₃ in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.     

Synthesis and structural characterization of trinuclear Cu(II)-pyrazolato complexes containing mu(3)-OH, mu(3)-O, and mu(3)-Cl ligands. Magnetic susceptibility study of [PPN](2)[(mu(3)-O)Cu(3)(mu-pz)(3)Cl(3)

The nine-membered [-Cu(II)-N-N-](3) ring of trimeric copper-pyrazolato complexes provides a sturdy framework on which water is twice deprotonated in consecutive steps, forming mu(3)-OH and mu(3)-O species. In the presence of excess chlorides the mu(3)-O(H) ligand is replaced by two mu(3)-Cl ions. The interconversion of mu(3)-OH and mu(3)-O and the exchange of mu(3)-O(H) and mu(3)-Cl are reversible, and the three species involved have been structurally characterized: [PPN][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(thf)].CH(2)Cl(2) (1a), monoclinic P2(1)/n, a = 10.055(2) A, b = 35.428(5) A, c = 15.153(2) A, beta = 93.802(3) degrees, V = 5386(1) A(3), Z = 4; [Bu(4)N][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)] (1b), triclinic P-1, a = 9.135(2) A, b = 13.631(2) A, c = 14.510(2) A, alpha = 67.393(2) degrees, beta = 87.979(2) degrees, gamma = 80.268(3) degrees, V = 1643.2(4) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-O)(mu-pz)(3)Cl(3)] (2), monoclinic P2/c, a = 12.807(2) A, b = 13.093(2) A, c = 23.139(4) A, beta = 105.391(3) degrees, V = 3741(1) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)].0.75H(2)O.0.5CH(2)Cl(2) (3a), triclinic P-1, a = 14.042(2) A, b = 23.978(4) A, c = 25.195(4) A, alpha = 76.796(3) degrees, beta = 79.506(3) degrees, gamma = 77.629(3) degrees, V = 7988(2) A(3), Z = 4; [Bu(4)N](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)] (3b), monoclinic C2/c, a = 17.220(2) A, b = 15.606(2) A, c = 20.133(2) A, beta = 103.057(2) degrees, V = 5270(1) A(3), Z = 4; [Et(3)NH][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(pzH)] (4), triclinic P-1, a = 11.498(2) A, b = 11.499(2) A, c = 12.186(2) A, alpha = 66.475(3) degrees, beta = 64.279(3) degrees, gamma = 80.183(3) degrees, V = 1331.0(5) A(3), Z = 2. Magnetic susceptibility measurements show that the three copper centers of 2 are strongly antiferromagnetically coupled with J(Cu-Cu) = -500 cm(-1).     

Cluster-type basic lanthanide iodides [M6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 (M = Nd, Eu, Tb, Dy)

Ln6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)(8) (Ln = Nd, Eu, Tb, Dy) compounds are obtained as the final hydrolysis products of lanthanide triiodides in an aqueous solution. Their X-ray crystal structure features a body-centered arrangement of oxygen-centered {Ln6X8}8+ cluster cores: [Nd6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1310.4(3) pm, b = 1502.1(3) pm, c = 1514.9(3) pm, 3384 reflections with I0 > 2sigma(I0), R1 = 0.0340, wR2 = 0.0764, GOF = 1.022, T = 298(2) K], [Eu6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1306.6(2) pm, b = 1498.15(19) pm, c = 1499.41(18) pm, 4262 reflections with I0 > 2sigma(I0), R1 = 0.0540, wR2 = 0.0860, GOF = 0.910, T = 298(2) K], [Tb6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 4182 reflections with I0 > 2sigma(I0), R1 = 0.0395, wR2 = 0.0924, GOF = 1.000, T = 298(2) K], and [Dy6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 3329 reflections with I0 > 2sigma(I0), R1 = 0.0389, wR2 = 0.0801, GOF = 0.992, T = 298(2) K.     

Aluminosilicate relatives: Chalcogenoaluminogermanates Rb(3)(AlQ(2))(3)(GeQ(2))(7) (Q = S, Se)

The new compounds Rb(3)(AlQ(2))(3)(GeQ(2))(7) [Q = S (1), Se (2)] feature the 3D anionic open framework [(AlQ(2))(3)(GeQ(2))(7)](3-) in which aluminum and germanium share tetrahedral coordination sites. Rb ions are located in channels formed by the connection of 8, 10, and 16 (Ge/Al)S(4) tetrahedra. The isostructural sulfur and selenium derivatives crystallize in the space group P2(1)/c. 1: a = 6.7537(3) ?, b = 37.7825(19) ?, c = 6.7515(3) ?, and β = 90.655(4)°. 2: a = 7.0580(5) ?, b = 39.419(2) ?, c = 7.0412(4) ?, β = 90.360(5)°, and Z = 2 at 190(2) K. The band gaps of the congruently melting chalcogenogermanates are 3.1 eV (1) and 2.4 eV (2).     

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) ?, b = 11.949(3) ?, c = 9.737(1) ?, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) ?, b = 7.861(7) ?, c = 16.24(2) ?, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) ?, b = 13.885(2) ?, c = 7.900(4) ?, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.     

Phosphanimin- und Phosphaniminato-Komplexe von Magnesium. Die Kristallstrukturen von [MgBr1,25I0,75(Me3SiNPMe3)(OEt2)], [MgI2(Me3SiNPMe3)2], [Mg2I2(Me3SiNPMe2CH2)Me3SiNPMe2CH2CH(Me)O)(OEt2)] und [MgBr(NPMe3)]4·C7H8

Phosphaneimine and Phosphoraneiminato Complexes of Magnesium. The Crystal Structures of [MgBr_1,25I_0,75(Me₃SiNPMe₃)(OEt₂)], [MgI₂(Me₃SiNPMe₃)₂], [Mg₂I₂(Me₃SiNPMe₂CH₂)(Me₃SiNPMe₂CH₂CH(Me)O)(OEt₂)], and [MgBr(NPMe₃)]₄ · C₇H₈ By reactions of the silylated phosphaneimine Me₃SiNPMe₃ with the Grignard reagents EtMgBr and MeMgI, respectively, the carbanionic phosphoraneiminato derivatives [XMg(CH₂PMe₂NSiMe₃)]_n (X ? Br, I) can be isolated as main products. The by-products of these reactions, [MgBr_1.25I_0.75(Me₃SiNPMe₃)(OEt₂)], [MgI₂(Me₃SiNPMe₃)₂] and [Mg₂I₂(CH₂PMe₂NSiMe₃)(O(Me)CHCH₂PMe₂NSiMe₃)(OEt₂)] were identified by crystal structure determinations. The phosphoraneiminato complex [MgBr(NPMe₃)]₄ · C₇H₈ with hetero cubane structure is formed by a metathesis reaction of [ZnBr(NPMe₃)]₄ with RMgBr (R ? Ph. Mes).