Reaction of 2 molar equiv of 2,6-di(1′-naphthyl)phenyllithium with bis[bis(trimethylsilyl)amino]germylene afforded the red, crystalline, stable bis[2,6-bis(1-naphthyl)phenyl]germylene [(bisap) 2 Ge, 6] in good yield. The structure of the solvate 6‚C 6 H 6 was determined by singlecrystal X-ray methods. The molecule features a largely strain-free conformation with a C-Ge-C angle of 102.72(9)°and Ge-C distances of 2.036(2) and 2.030(2) Å. These parameters are very close to those calculated for the diphenylgermylene prototype by ab initio methods [101.6°; 2.006 Å]. The two new wing-like 2,6-di(1-naphthyl)phenyl substituents appear to protect the germylene center of 6 in a very efficient way without inducing destabilizing distortions. Bis[2,4,germylene [(triph) 2 Ge, 1] was also prepared. Germylenes 1 and 6 were oxidized to yellow products of the composition (triph) 2 GeO (2) and (bisap) 2 GeO (7), respectively. The compounds have been characterized by their mass spectra, which show the parent ions in full accordance with the proposed formulas.

Arylgermanes of the types ArGeH 3 , Ar 2 GeH 2 , and Ar 3 GeH are important precursors for the preparation of oligo-and polygermanes. These precursors are readily prepared in good yields via an in situ Grignard reaction employing tetra(ethoxy)germane, an aryl halide, and magnesium metal in tetrahydrofuran as the reaction medium. The aryl-tri(ethoxy)germanes obtained were reduced to the germane hydrides with LiAlH 4 . This method is also applicable for aryl groups with sensitive substituents, as demonstrated for (4-methoxyphenyl)germane (p-anisylgermane, MeOC 6 H 4 GeH 3 ). With modified stoichiometry, bis(p-anisyl)germane is also available. The insertion of GeCl 2 into the C-Br bond of arylbromides using catalytic amounts of anhydrous AlCl 3 proved to be an efficient alternative if the reaction was carried out in the absence of a solvent. After LiAlH 4 reduction of the aryltrihalogermanes, phenyl-, p-tolyl-, and mesitylgermane were obtained in good yields. The arylgermanes have been identified by their analytical and spectroscopic data, including 73 Ge (s ) 9/2) NMR spectroscopy. Very surprisingly, sharp multiplet signals were observed with well-resolved 1 J(Ge,H) couplings. The molecular structure of p-MeOC 6 H 4 GeH 3 was determined from low-temperature X-ray diffraction data collected from a single-crystal grown "in situ" from the melt (mp: 15°C). The significant distortions observed in the anisyl part of the structure and the conformation of the molecule are in excellent agreement with results of ab initio quantum chemical calculations (MP2/6-31G*) of this compound.

The reaction of equimolar quantities of G eC h • dioxane with [BzEt3N]+ C P in tetrahydronaphthaline gives high yields of [BzEt3N]+ [G eC h]~. The asymmetric unit of the monoclinic single crystals (from CH 2 CI2 , space group P2i/c, Z = 8) are comprising two pairs of crystallo graphically independent cations and anions, each with very similar molecular dimensions. The isolated [G eC b]-anions have a trigonal pyramidal structure with narrow Cl-Ge-Cl angles in the range from 93.41(5) to 98.27(5)° and Ge-Cl distances between 2.293(2) and 2.305(2) A. This structure is thus very similar to that of the isoelectronic A sCb molecule and of the [SeCl3 ]+ cation.

Germylenes, Germanium(II) Amides, Sulfurization Treatment of bis[bis(trimethylsilyl)amino]germanium(II) with elemental sulfur or sele nium affords high yields of the corresponding monosulfide [(Me.^Si^NLGeS and selenide [(M e.^SihN^GeSe, respectively. The crystalline products have now been shown to be cyclic dimers with (GeS/Se)2 four-membered rings by X-ray single crystal structure analysis. The crystal structure of (triphenylphosphine)gold(I) bis(trimethylsilyl)amide (Ph;?P)Au-N(SiMe3)2 has also been determined. The molecule is a monomer with a tricoordinate nitrogen atom in a planar configuration [SiiNAu]. The compound does not undergo insertion of the bis[bis(trimethylsilyl)amino]germylene.

1 -Iodo-2,6-bis(4-methoxy-phenyl)benzene (BipapI) was prepared in a Grignard reaction from 4-bromo-anisol and 2,6-dibrom o-1 -iodo-benzene in tetrahydrofuran (61% yield). Treatment of BipapI with Az-butyllithium in hexane/diethylether gave the corresponding terphenyl-lithium compound BipapLi which crystallized as the dietherate in 83% yield. The structure of BipapLi • (OE2)2 has been determined by single crystal X-ray methods. The molecule is a monomer in the lattice, and the lithium atom is three-coordinate. Preparation of BipapLi in the presence of PbCl2 in diethylether gave a green solution, from which yellow crystalline (n -Bu)(Bipap)2Pbl was isolated in 73% yield. In the crystal this triorganolead(IV) iodide is monomeric and has tetrahedrally four-coordinate lead atoms.