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 reaction of (phenylacetylenyl)triethoxygermane, (EtO)(3)GeCdropCPh (3), with bromine in CHCl3/CCl4 solution leads to a mixture of Z- and E- (EtO)(3)GeC(Br)=C(Br)Ph (4) in the ratio Z/E = 3/1. Treatment of this product with N(CH2CH2OH)(3) affords a mixture of Z- and E-N(CH2CH2O)(3)GeC(Br)=C(Br)Ph (2) in high yield. Compound E-2 was isolated in 16% yield. The molecular composition and the structure of all new compounds have been established by elemental analyses, H-1 and C-13 NMR spectroscopy. The crystal structure of E-2 is reported. The possible reasons for the different Z/E ratios in the products of the bromination of 3 and N(CH2CH2O)(3)GeC=CPh (1) are discussed using DFT calculations.

The reaction of (phenylacetylenyl)triethoxygermane, (EtO)3GeC≡CPh (3), with bromine in CHCl3/CCl4 solution leads to a mixture of Z- and E- (EtO)3GeC(Br)=C(Br)Ph (4) in the ratio Z/E = 3/1. Treatment of this product with N(CH2CH2OH)3 affords a mixture of Z- and EN(CH2CH2O)3GeC(Br)=C(Br)Ph (2) in high yield. Compound E-2 was isolated in 16% yield. The molecular composition and the structure of all new compounds have been established by elemental analyses, 1H and 13C NMR spectroscopy. The crystal structure of E-2 is reported. The possible reasons for the different Z/E ratios in the products of the bromination of 3 and N(CH2CH2O)3GeC≡CPh (1) are discussed using DFT calculations.

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.

The reaction of C(NMe 2 ) 4 (1) with M(CO) 6 (M = Cr, W) in THF solution leads to the anionic carbamoyl complexes [C(NMe 2 ) 3 ][(CO) 5 MC(O)NMe 2 ] (2a, M = Cr; 2c M = W). In the case of M = Mo the resulting complex 2b is not obtained; instead, the salts [C(NMe 2 ) 3 ]2[Mo 2 (CO) 10 ] (3) and [C(NMe 2 ) 3 ][(CO) 4 Mo(O 2 CNMe 2 )] (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.

Abstract 1,2,3,4-Tetraisopropylcyclopenta-2,4-dien-1-yl arsenic (III) dihalides, viz. TipCpAsX2 (1 X = Br, 2 X = I), have been prepared by direct metathesis reaction between the corresponding arsenic (III) trihalides with one equivalent of TipCpK at low temperature in good yields. Alternatively, 2 has been prepared via halogen exchange reaction between TipCpAsCl2 (3) and KI. New compounds have been characterised by spectroscopic m ethods ( 1H, 13C NMR. EI-MS) and elemental analyses. The crystal structures of 1 and 2 have been determined by X-ray diffraction methods. The AsX2-moiety in 1 and 2 occupies an allylic position neighbouring to an isopropyl substituent. The arsenic fragment is o-bound to the cyclopentadienyl ligand, indicating remarkable π-interactions with the diene part of the cyclopentadienyl ring.

The reaction of with yielded [I], the first organobismuth compound with -bonded cyclopentadienyl ring. The compound I which was the violet crystal (yield, 30%) was decomposed to . The Structure of was identified as single crystal by X-ray diffraction method. The eliminated product , triclinic crystal of space group p1(Z=2) which was attached with C-C -bond of two cyclopentadienyl was defined by the structural analysis.

Abstract 1,2,3,4-Tetrakis(t-butyl)tetraarsetane (t-C4H9As)4(4) has been synthesized by reduction of t-butylarsenic (III) diiodide (1) with equivalent quantities of either Mg, Ca, Zn, Li, or CoCp2 in THF at low temperatures in high yields. Treatment of 1 with CoCp2 in a molar ratio 1:1 in n-pentane at -78 °C leads to the formation of 1,2-di-t-butyl-1,2-diiododiarsine (2) (t-C4H9AsI)2 in 69 % yield. The products have been characterized by spectroscopic methods (H, 13C-NMR, EI-MS) and elemental analyses. The crystal structure of 2 has been determined by X-ray diffraction methods.

A series of polyelement substituted cyclopentadienyl and indenyl boranes and arsanes containing Me3Si-, Me3Sn- was synthesised; (C5H4SiMe3)BX2 (2, X = Cl; 3, X = Br) and (C9H6SiMe3)BX2 (4, X = Cl; 5, X = Br) were obtained by Si/B exchange reaction in a low yield when X = Cl and in a moderate yield when X = Br, whereas Flu(SIMe3)2 does not react with BBr3 at all. PhB(C5H4SiMe3)2 (6) and PhB[C5H3(SiMe3)2]2 (7) were synthesised using appropriate thallium cyclopentadienides in high yields, 81% and 99% respectively. More bulky indenyl derivatives TrsB(C9H7)2 (8, Trs = (Me3Si)3C—), PhB(C9H6SiMe3)2 (9), Ph2B(C9H6SiMe3) (10) were prepared by metathesis reactions of lithium indenides with boron halides in high yields. A subsequent transmetallation of C9H6(SnMe3)2 with PhBCl2 followed by addition of ZrCl4 gave (η5-C9H6SnMe2Cl)2ZrCl2 (11) in the form of one of two possible diastereomers in high yield. C9H6(SiMe3)SnMe3 reacts with BCl3 to give the appropriate bis-indenyl derivative, that was easily converted to the ansa-zirconocene complex [MeB(η5-C9H6)2]ZrCl2 (12). The sterically demanding bis-indenyl ligand 8 underwent direct deprotonation by t-BuLi, affording [TrsB(η5-C9H6)2]ZrCl2 (13) by in situ reaction with Me3SnCl and ZrCl4. Indenylarsanes (C9H7)3As (14), t-BuAs(C9H7)2 (15), C9H7AsMe2 (16) and (C9H6SiMe3)AsMe2 (17) were synthesised by reactions of lithium indenides with asenic halides in good to excellent yields. All these compounds were characterized by analytical and spectroscopic data (NMR, MS). 14 and 15 exist as complex isomeric mixtures with the arsenic atom in the allylic position of the indenyl ring; the crystal structure of a meso form of 15 was determined by X-ray diffraction methods. 17 consists of two isomers with a vinylic (17a) and an allylic (17b) Me3Si substituent. Stannylation of 16 by Me3SnNEt2 led exclusively to the diallylic derivative (C9H6AsMe2)SnMe3 (18) in quantitative yield. The latter was readily converted to a polymeric, half-sandwich indenyl zirconocene [η5-(C9H6AsMe2)ZrCI3]n (19) in high yield. Further reaction of 19 with Cp★ Li resulted in the formation of a new arsano substituted bent metallocene complex [η5-(C9H6AsMe2)-η5-(C5Me5)]ZrCl2 (20) in good yield.

Tin-119 and phosphorus-31 NMR spectra have been recoreded for three tin tetrahalide complexes with tetraethyl propylenediphosphonate SnX4 · L, where L = (EtO)2P(O)CH2 CHMeP(O) (OEt)2, X = Cl (1); X = Br(2); X = I(3). Each complex exists in solution in the form of only one isomer with two different phosphoryl units coordinated at tin. The crystal structure of SnCl4 · L (1) has been determined. The complex has a monomeric 7-membered chelate structure with octahedral environment at tin. It crystallizes in the monoclinic space group P21/n with a = 9.531(2) A, b = 16.556(3)A, c = 14.634(3) A, β = 98.73(3)°, Z = 4, d calc = 1.678 Mg/m3, N obs = 2813, R = 0.045.

1,2,3,4-Tetrakis(t-butyl)tetraarsetane (t-C 4 H 9 As) 4 (4) has been synthesized by reduction of t-butylarsenic (III) diiodide (1) with equivalent quantities of either Mg, Ca, Zn, Li, or CoCp 2 in THF at low temperatures in high yields. Treatment of 1 with CoCp 2 in a molar ratio 1:1 in n-pentane at -78 °C leads to the formation of 1,2-di-t-butyl-1,2-diiododiarsine (2) (t-C 4 H 9 AsI) 2 in 69 % yield. The products have been characterized by spectroscopic methods (H, 13 C-NMR, EI-MS) and elemental analyses. The crystal structure of 2 has been determined by X-ray diffraction methods.