The title compound, viz. (C6F5)(2)NLi was prepared as dimeric complexes with Et2O or THF by the reaction Of (C6F5)(2)NH (DFDPA) with n-BuLi. Identity and structures were established by elemental analyses, H-1, C-13, and F-19 NMR spectroscopy, and IR spectroscopy. The crystal structures of dimeric [(C6F5)(2)NLi(Et2O)](2) (1) and [(C6F5)(2)NLi(THF)](2) (2) were determined by X-ray diffraction methods.

[In(NEt2)(3)](2) and N(CH2CH2NSiMe3H)(3) react to yield monomeric azaindatrane 1, N(CH2CH2NSiMe3)(3)In, which is unstable without additional donor (e.g. pyridine), turning into dimeric azaindatrane 2, [N(CH2CH2NSiMe3)(2)(CH2CH2NH)In](2). An intermediate product of this transformation is oligomeric azaindocane 3, [N(CH2CH2NSiMe3)(2)In(CH2CH2NSiMe3)](3). The composition and structures of new compounds have been established by H-1 and C-13 NMR spectroscopy. The crystal structures of 1(.)Py, trans-2, and 3 have been determined by X-ray diffraction studies. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Antimony tris-amides-(Et2N)(3-n)Sb[N(C6F5)(2-C5H4N)](n) [n = 1 (3), 2 (4) or 3 (5)]-have been prepared by treatment of Sb(NEt2)(3) (1) with stoichiometric amounts of (2-C5H4N)(C6F5)NH (2). In contrast to amide 5, compounds 3 and 4 are unexpectedly unstable and react further to give the bis-amido antimony fluorides [(2-Et2N-C6F4)(2-C5H4N)N]Sb(F)[N(C2H5)(2)] (6) and [(2-Et2N-C6F4)(2-C5H4N)N]Sb(F)[N(C6F5)(2-C5H4N)] (7). The structure of 7 was confirmed by X-ray diffraction studies. DFT calculations, which reproduce the principal features of compound 7's geometry, have been used to explain the possible reaction pathway of this ortho-directed metathetical fluoride-amide exchange. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Reactions of element-substituted alkynes R(3)MCdropCPh (R3M=Me3Si, Et3Si, Ph3Si, Et3Ge, n-Bu3Sn, N(CH2CH2O)(3)Si, N(CH2CH2O)(3)Ge, N(CH2CHMeO)3Ge, and N(CH2CH2O)(2)(CH2CHPhO)Ge) with bromine, tetra-n-butylammonium tribromide (TBAT), and N-bromosuccinimide (NBS)/DMSO were investigated. The Z,E-ratio of isomeric dibromoalkenes formed in bromination reaction with Br-2 and TBAT are discussed. The crystal structures of N(CH2CH2O)(3)SiCdropCPh and N(CH2CHMeO)(3)GeX (X=CdropCPh, C(Br)=C(Br)Ph, C(Br-2)C(O)Ph), and Ph3SiC(Br)=C(Br)Ph are reported. (C) 2003 Wiley Periodicals, Inc.

We present the results of the epitaxial overgrowth of magnetic (MnGa)As-cluster structures with GaAs, (AlGa)As and AlAs using metal organic vapor phase epitaxy (MOVPE). The structural differences in the overgrowth are investigated by means of atomic force microscopy (AFM) combined with transmission electron microscopy (TEM), in particular, to proof the successful overgrowth of the cluster layers with AlAs. Out of these experiments a first model for the overgrowth is developed. Measurements using a SQUID-magnetometer confirm the existence of ferromagnetism above room temperature in the cluster layers after overgrowth; however, other magnetic properties as the coercitive field are influenced by the overgrowth process.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The reaction of GeHal4 with MeN(CH2CH2OSiMe3)2 affords dihalogermocanes MeN(CH2 CH2O)2GeHal2 (1, Hal = Br; 2, Hal = Cl). Treatment of Me2Ge(NMe2)2 with MeN(CH2CH2OH)2 leads to dimethylgermocane MeN(CH2CH2O)2GeMe2 (3). The composition and structure of 1-3 were established by elemental analyses, 1H, 13C NMR spectroscopy, and mass spectrometry. The crystal structure of 1 is reported; structural data obtained from geometry DFT optimization on 1 are in good agreement with experimental results. Values of the electron density in the N→Ge bond critical point and the Laplacian of charge density for 1-3 indicate a closed-shell interaction between the Ge and N atoms.

Syntheses of a series of the title compounds, viz., N(CH2CH2NR)(3)M-X (1, M = Si, X = Me, R = SiMe3; 2, M = Si, X = Et, R = SiMe3; 3, M = Si, X = n-Bu, R = SiMe3; 4, M = Si, X = vinyl, R = SiMe3; 5, M = Si, X = Ph, R = SiMe3; 6, M = Ge, X = Me, R = SiMe3; 7, M = Ge, X = n-Bu, R = SiMe3; 8, M = Ge, X = Ph, R = SiMe3; 9, M = Sn, X = n-Bu, R = SiMe3; 10, M = Sn, X = Ph, R = SiMe3; 11, M = Si, X = vinyl, R = Me; 12, M = Ge, X = Me, R = Me) by the reaction of X-MCl3 with N(CH2CH2NSiMe3Li)(3) or with N(CH2CH2NMeLi)(3) are reported. Reactions of the novel compounds X-Ge(NMe2)(3) (15, X = Ph; 16, X = 1-naphthyl; 17, X = 9-antracenyl; 18, X = 9-phenantrenyl) with N(CH2CH2NHMe)(3) or N(CH2CH2NH2)(3) resulted in new 1-arylazagermatranes, N(CH2CH2NMe)(3)Ge-X (19, X = Ph; 20, X = 1-naphthyl; 21, X = 9-antracenyl; 22, X = 9-phenantrenyl) and N(CH2CH2NH)(3)Ge-X (23, X = Ph; 24, X = 1-naphthyl; 25, X = 9-phenantrenyl), respectively. 1-Phenylazager-matrane (23) is transformed to 8 by treatment with n-BuLi/Me3SiCl. Composition and structures of novel compounds were established by elemental analyses, H-1, C-13, and Si-29 NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly indicated the presence of a transannular interaction M<--N-ax for both compounds. quasi-Azametallatranes 5 and 8 possess extremely long M<--N-ax distances.

Reaction of excess of product A [(HOCH2CH2)2NCH2CH(Ph)OH (1):(HOCH2CH2)2NCH(Ph)CH2OH (2)=9:1] with GeCl4 led to a mixture of 1-chloro-3-phenylgermatrane (3) and 1-chloro-4-phenylgermatrane (4). Compound 4 was isolated in yield 9% from this mixture. Reaction of (EtO)3GeCl with product A gave 3 in yield 55%. 1-(Phenylethynyl)-3-phenylgermatrane (5) was prepared in yield 31% by treatment of (EtO)3GeCCPh with product A. Reaction of product A with mixture of GeO2 and H2O produced N(CH2CH2O)2(CH2CHPhO)GeOH (6) in yield 73%. The presence of N(CH2CH2O)2(CHPhCH2O)GeOH (7) among the products of this reaction was confirmed by 1H-, 13C-NMR spectroscopy and X-ray analysis. N(CH2CH2O)2(CH2CHPhO)GeF (8) is formed by the treatment of 6 with BF3·Et2O. N(CH2CH2O)2(CH2CHPhO)GeOSiMe3 (9) was obtained by silylation of 6 with (Me3Si)2NH or Me3SiCl–Et3N. Refluxing of a suspension of 6 in xylene with continuous removal of water by azeotropic distillation afforded [N(CH2CH2O)2(CH2CHPhO)Ge]2O (10). 9 reacted with SOCl2, Me3SiBr and Me3SiOTf to give N(CH2CH2O)2(CH2CHPhO)GeX (3, X=Cl; 11, X=Br; 12, X=OTf), respectively. Reaction of 11 with Et3SnOMe led to the formation of N(CH2CH2O)2(CH2CHPhO)GeOMe (13). Germatranes N(CH2CH2O)2(CH2CHPhO)GeY [14, Y=Flu (fluorenyl); 15, Y=N(SiMe3)2] were obtained from the nucleophilic substitution of the substituent X in N(CH2CH2O)2(CH2CHPhO)GeX (X=OSiMe3, Br) with the corresponding LiY. All compounds were characterized by 1H- and 13C-NMR spectroscopy and mass spectrometry. Single-crystal structures of 5 and 7–9 were determined by X-ray diffraction studies.

Single crystal structures of N(CH2CH2NSiMe3)3Si-Vinyl (1) and N(CH2CH2NSiMe3)3Si-n-Butyl (2) were determined by X-ray diffraction studies: both compounds show weak transannular Nax→M interactions (1, d(Nax→Si)=2.712(1) Å, 2, d(Nax→Ge)=2.743(3) Å). General trends for molecular structures of the group 14 elements (Si, Ge, Sn) azametallatranes are discussed with also included DFT calculations data.

The reaction between MHal4 (M = Ge, Sn; Hal = Cl, Br) and N(CH2CH2NRLi)3 (R = Me, SiMe3) yields 1-haloazametallatranes 1−8, N(CH2CH2NR)3M−Hal (1, M = Ge, Hal = Cl, R = Me; 2, M = Ge, Hal = Br, R = Me; 3, M = Ge, Hal = Cl, R = SiMe3; 4, M = Ge, Hal = Br, R = SiMe3; 5, M = Sn, Hal = Cl, R = Me; 6, M = Sn, Hal = Br, R = Me; 7, M = Sn, Hal = Cl, R = SiMe3; 8, M = Sn, Hal = Br, R = SiMe3). The composition and structures of the new compounds were established by elemental analyses, 1H and 13C NMR spectroscopy and mass spectrometry. Single crystal structures of 1 and 3 were determined by X-ray diffraction studies: both compounds show transannular Ge−Nax interactions. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Syntheses of title compounds, viz. N(CH2CH2NR)3E (1, E = Sb, R = Me; 4, E = Bi, R = Me; 6, E = Sb, R = SiMe3; 8, E = Bi, R = SiMe3), by the reaction of E(NAlk2)3 (3, E = Sb, Alk = Et; 5, E = Bi, Alk = Me) with N(CH2CH2NMeH)3 (2) or N(CH2CH2NSiMe3H)3 (7) are reported. The reactions of SbCl3 with N[CH2CH2N(Me)Li]3 or N[CH2CH2N(SiMe3)Li]3 and BiCl3 with N[CH2CH2N(SiMe3)Li]3 resulted in compounds 1, 6, and 8, respectively. Composition and structures of all novel compounds were established by 1H and 13C NMR spectroscopy and mass spectrometry. The X-ray structural study of 8 clearly indicated the presence of transannular interaction BiNdat in this compound, while 6 possesses a long Sb...Ndat distance. The structural data obtained from geometry optimizations on 6 and 8 reproduce experimental trends, i.e., a decrease in the E-Ndat distance from Sb to Bi. The values of electron density in E-Ndat critical point and the Laplacian of charge density for 8 indicate that a closed-shell interaction exists between the metal atom and Ndat atom.

The reaction of 1-phenylgermatrane (1) and 1-phenylazagermatrane (2) with Cr(CO)6 affords chromium tricarbonyl complexes [N(CH2CH2O)3GeC6H5]Cr(CO)3 (6) and [N(CH2- CH2NH)3GeC6H5]Cr(CO)3 (7). In contrast, the same reaction of Cr(CO)6 with 1-(9-anthracenyl) germatrane (3) does not proceed. Composition and structures of the 6 and 7 were established by elemental analyses, 1H and 13C NMR spectroscopy and mass spectrometry. The crystal structure of 6 is reported

We present the results of the successful epitaxial growth of magnetic MnGaAs-cluster structures using metal organic vapour phase epitaxy (MOVPE). Investigations by SQUID-magnetometer established ferromagnetism with Curie temperature as high as 320 K, clear in-plane anisotropic magnetic behavior is detected. The structural properties of the epitaxial layers are investigated by means of atomic force microscopy (AFM) and in particular transmission electron microscopy (TEM). A statistical analysis of the cluster sizes shows, that the clusters expand strongly with increasing deposition temperature, whereas the part of the surface, covered with clusters, stays constant at 25 +/-5 %. Preliminary experiments show that the MnGaAs clusters can be overgrown and embedded defect-free in host (AlGa)As layer structures.

Reaction of N(CH2CHRO)3GeBr (2a, b) with LiCCPh affords N(CH2CHRO)3GeCCPh (1a, b) (a, R=H; b, R=Me). Compound (1b) was also obtained by treatment of Cl3GeCCPh (3) with N(CH2CHMeOSnEt3)3 (4). (1a) reacts with N-bromosuccinimide to yield N(CH2CH2O)3GeC(Br)2C(O)Ph (5). Cis-N(CH2CH2O)3GeC(Br)C(Br)Ph (6) is formed by the reaction of 1a with Br2 in equivalent amounts. All compounds were characterized by 1H- and 13C-NMR spectroscopy and mass spectrometry. Single crystal structures of 1a and 6 were determined by X-ray diffraction studies.

The reaction of C(NMe2)(4) (1) with M(CO)(6) (M = Cr, W) in THF solution leads to the anionic carbamoyl complexes [C(NMe2)(3)] [(CO)(5)MC(O)NMe2] (2a, M = Cr; 2c M = W). In the case of M = Mo the resulting complex 2b is not obtained; instead, the salts [C(NMe2)(3)](2)[Mo-2(CO) (10)] (3) and [C(NMe2)(3)] [(CO)(4)Mo(O2CNMe2)] (4) are isolated. The crystal structures of 2a, 3, and 4 are presented. In the salt-like compounds no interatomic contacts between anion and cation exist, and the cations are disordered. The structure of 4 shows two independent molecules. The compounds were further characterized by IR and NMR spectroscopy.

The reaction of tris(dimethylamino)halogermanes, (Me2N)(3)GeHal(7, Hal = C1; 8, Hal = Br), with tris(2-aminoethyl)amines, N(CH2CH2NHR)(3) (5, R = H; 6, R = Me), yield 1-halo-N,N',N"- azagermatranes (1, X = Cl, R = H; 2, X = Br, R = H; 3, X = Cl, R = Me; 4, X = Br, R = Me). Treatment of 4 with n-butyllithium affords 1-n-butyl-N,N',N"-trimethylazagermatrane (14) in high yield. Reactions of n-BuLi with 7 or (Me2N)(4)Ge (13) lead to the formation of (Me2N)(3)Ge n-Bu (15). On treatment of 15 with 5 the I -n-butylazagermatrane 16 was obtained. The molecular composition and the structures of all new compounds were established by elemental analyses, H-1 and C-13 NMR spectroscopy and mass spectrometry.

New germatranes N(CH2CHRO)3GeOTf (4a, R=H; 4b, R=Me) were prepared in quantitative yield by treatment of N(CH2CHRO)3GeOSiMe3 (2a and 2b), with Me3SiOTf. The reactions of germatranes N(CH2CHRO)3GeX [3a, X=Br, R=H; 4a, X=OSO2CF3, R=H; 4b, X=OSO2CF3, R=Me; 2a, X=OSiMe3, R=H; 2b, X=OSiMe3, R=Me] with LiY reagents were studied. A series of germatranes N(CH2CHRO)3GeY [5a, R=H, Y=Ind (indenyl); 5b, R=Me, Y=Ind; 6a, R=H, Y=N(SiMe3)2; 6b, R=Me, Y=N(SiMe3)2; 7a, R=H, Y=Cp (cyclopentadienyl); 7b, R=Me, Y=Cp; 8a, R=H, Y=Flu (fluorenyl); 9a, R=H, Y=t-Bu] were obtained by nucleophilic substitution with the corresponding LiY reagent. Reactions of N(CH2CHMeO)3GeOSiMe3 (2b) and N(CH2CH2O)3GeBr (3a) with excess n-BuLi and of N(CH2CH2O)3GeOSiMe3 (2a) with excess LiNMe2 led to the formation of n-Bu4Ge and (Me2N)4Ge. The structures of new germatranes 4a, 4b, 6b and 7b were confirmed by NMR spectroscopy, mass spectrometry and elemental analyses.

For the first time, a successful growth of Ga1−xMnxAs layers on (100)GaAs substrates by metal-organic vapour-phase epitaxy is reported. Optical and magneto-optical spectroscopy of the E0, E1 and E1+Δ1 transitions is possible due to the high structural quality of the samples. A strong exchange interaction is found in the Ga1−xMnxAs layers between the magnetic moments of manganese and the excitonic states, which exhibits an effective ferromagnetic coupling. The Mn concentrations in the layers can be estimated by two different and independent optical methods (i) from the Zeeman splitting of the E0 excitons and (ii) from the red-shift of the E1 transition due to the p-doping with Mn.