The reactions of [In(NEt2)(3)](2) and Sb(NEt2)(3) With an equimolar amount of decafluorodiphenylamine (DFDPA, LH) lead to the indium or antimony amides [(C6F5)(2)NIn(NEt2)(2)](2) (1) and (C6F5)(2)NSb(NEt2)(2) (2). Compound 2 rearranged further to give monofluoride Et2NSb(F)[N(o-Et2N-C6F4)(C6F5)] (3) and then difluoride F2Sb[N(o-Et2N-C6F4)(2)](4). The hydrolysis of 4 gave free ligand HN(o-Et2N-C6F4)(2) (5). Closely related HN(o-Me2N-C6F4)(2) (6) was prepared from the reaction of Bi(NMe2)(3) with DFDPA. The reactions of LiN(C6F5)(2)center dot THF with metal halides gave Sb[N(C6F5)(2)](3) (7), Me3Sb(Br)[N(C6F5)(2)] (8), Me3Sb(Cl)[N(C6F5)(2)] (9), Me3Sb[N(C6F5)(2)](2) (10), [Li(THF)(2)][In{N(C6F5)(2)}(3)Cl] (11). The X-ray structural investigations of 2 and 8 are presented. (C) 2009 Elsevier B.V. All rights reserved.

The indium tris(amide)s [(Et2N)(3-n)In{N(C6F5)(2-C5H4N)}(n)] [n = 1 (15), 2 (16) or 3 (9)] have been prepared by treatment of [In(NEt2)(3)](2) (3) with a stoichiometric amount of (2-C5H4N)(C6F5)NH (1). The analogous reaction of Bi(NMe2)(3) (2) with 3 equiv. of amine I and the treatment of BiCl3 (5) with a stoichiometric amount of (2-C5H4N)(C6F5)NLi (4) both lead to [Bi{N(C6F5)(2-C5H4N)}(3)] (10). In contrast, only the difluoride 11 or the monofluoride 12, which are the products of intramolecular ortho-directed exchange of NMe2 and F substituents, are obtained from the reaction of 2 with 1 or 2 equiv. of 1, respectively. The reaction between Me3Sb(Hal)(2) [Hal = Br (7) Cl, (8)] and 1 or 2 equiv. of lithium salt 4 gives the corresponding stable monoamides [Me-3(Hal)Sb{N(C6F5)(2-C5H4N)}] [Hal = Br (17), Cl (18)] or bis(amide) [Me3Sb{N(C6F5)(2-C5H4N)}(2)] (19), respectively. The structure of 9 has been confirmed by an X-ray structure analysis, and density functional calculations data have been used to explain the possible reaction pathway of the ortho-directed metathetical fluoride/amide exchange. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

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.

The reaction between [In(NEt2)(3)](2) and N(CH2CH2NMeH)(3) yields the N,N',N"-trimethylazaindatrane dimer [N(CH2CH2NMe)(3)In](2) (1). The composition and structure of 1 were established by H-1 and C-13 NMR spectroscopy as well as by an X-ray diffraction study. The X-ray structure shows that both indium atoms are pentacoordinate, with widely differing In-N distances. The structural parameters of 1 were compared with those obtained from a computational study. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

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.

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.

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 reactivity of 1-(9-fluorenyl)germatrane (I) containing several reaction centers (the Ge-C apical bond, Ge-O equatorial bonds, mobile hydrogen atom in the 9-position of the fluorenyl group, and aromatic rings) is studied. Its interaction with reagents that could involve each of the centers is investigated. The reactivities of I and 9-trimethylgermylfluorene (II), a fluorenyl derivative of tetracoordinated germanium, are compared. Structure II is studied by X-ray crystallography. The crystals are orthorhombic: a = 6.393(6) Angstrom, b = 15.279(7) Angstrom, c = 14.263(7) Angstrom, V = 1393(2) Angstrom(3), Z = 4, space group P2(1)2(1)2(1). The coordination environment of the germanium atom in II is close to tetrahedral.

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 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.

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.