Desulfurization of isothiocyanates by a divalent germanium amide.

Ge[N(SiMe)] reacts with isocyanates but its reactivity with the related heavier congeners has not been explored. Its reaction with tertiary isothiocyanates results in the abstraction of the sulfur atom to yield a germanium(IV) dimer [((SiMe)N)GeS] in high yield. The reaction with -butylisoselenocyanate produced the related dimer [((SiMe)N)GeSe] within 5 minutes as shown using Se NMR spectroscopy.

Synthesis, Structure, Frontier Orbitals and Reactivity of PhGeN(SiMe): Rare Crystal Structure of a Germylamine.

The germylamine PhGeN(SiMe) was synthesized from PhGeCl and LiN(SiMe) and its X-ray crystal structure was determined. This structure represents only the fourth crystallographically characterized germylamine that has been reported. The two sterically encumbering -SiMe groups completely encapsulate the germanium-nitrogen bond and the geometry at the nitrogen atoms is trigonal planar rather than pyramidal.

Exploring the Versatility of the Amidation of Aryl Acid Fluorides using the Germylamines R GeNMe.

The formation of amide bonds is an important process since this linkage is an essential component in proteins, pharmaceuticals, and other medicinally and biologically significant molecules. Recently, it was demonstrated that germylamines R GeNR' were useful reagents for the conversion of acid fluorides to amides. This transformation occurs readily at room temperature and has a low activation energy.

Direct amidation of acid fluorides using germanium amides.

Amide functional groups are an essential linkage that are found in peptides, proteins, and pharmaceuticals and new methods are constantly being sought for their formation. Here, a new method for their preparation is presented where germanium amides PhGeNR convert acid fluorides directly to amides. These germanium amides serve to abstract the fluorine atom of the acid fluoride and transfer their amide group -NR to the carbonyl carbon, and so function as amidation reagents.

Transition metal-free hydrodefluorination of acid fluorides and organofluorines by PhGeH promoted by catalytic [PhC][B(CF)].

It has been shown that the germane Ph3GeH converts aryl and aliphatic acid fluorides directly to their corresponding aldehydes without over-reduction via the conversion of Ph3GeH to the germylium cation [Ph3Ge]+ by a catalytic amount of the tritylium salt [Ph3C][B(C6F5)4]. Here, no transition metal catalyst is required and there is no decarbonylation of the acid fluoride, which are advantages over existing methods. The fluorine atoms can also be abstracted from organofluorine compounds using this method.

A luminescent and dichroic hexagermane.

The hexagermane Pr(i)3Ge(GePh2)4GePr(i)3 has been synthesized and is not only the first such linear oligogermane to be structurally characterized but also is the first such compound to exhibit fluorescence and dichroic properties when observed under different orientations of plane polarized visible light.

A divalent germanium complex of calix[5]arene.

The reaction of the germylene Ge[N(SiMe(3))(2)](2) with calix[5]arene yields the first example of a group 14 calix[5]arene complex. The crystal structure of this material has been obtained and contains two calix[5]arene macrocycles held together by a Ge(2)O(2) rhombus.

Formation and structures of germanium(II) Aryloxo/oxo clusters.

The reaction of Ge[N(SiMe(3))(2)](2) with a phenol lacking a substituent in one ortho position results in the formation of polynuclear clusters having terminal aryloxide ligands and bridging O atoms. Structures of this type have not been observed for germanium(II) aryloxides before, and the source of the bridging O atoms in these clusters was determined to be the phenol reactant.

Syntheses, structures and properties of linear and branched oligogermanes.

This Perspective surveys recent developments in the synthesis and characterization of discrete oligogermanes. The use of the hydrogermolysis reaction, combined with a protection/deprotection strategy for a Ge-H moiety, has resulted in the synthesis of a variety of oligogermanes where the number of catenated atoms and the identity of the organic substituents can be readily controlled. Relationships between the composition of these oligomers and their optical and electronic properties have also been established.

2,2,3,3,5,5,6,6-Octa-p-tolyl-1,4-dioxa-2,3,5,6-tetra-germacyclo-hexane dichloro-methane disolvate.

The title compound, C(56)H(56)Ge(4)O(2)·2CH(2)Cl(2) or Tol(8)Ge(4)O(2)·2CH(2)Cl(2) (Tol = p-CH(3)C(6)H(4)), was obtained serendipitously during the attempted synthesis of a branched oligogermane from Tol(3)GeNMe(2) and PhGeH(3). The mol-ecule contains an inversion center in the middle of the Ge(4)O(2) ring which is in a chair conformation. The Ge-Ge bond distance is 2.

Metal-dependent reactions of bulky metal(II) amides M[N(SiMe3)2]2 with 3,3'-disubstituted binaphthols (HO)2C20H10(SiR3)2-3,3': selective conversion of one equivalent -OH group to a silyl ether -OSiMe3.

The outcome of the reaction of the bulky metal(II) amides M[N(SiMe3)2]2. nTHF (M = Be, Zn, Ge, Sn, n = 0; M = Mg, Ca, n = 2) with (R)-3,3'-bis(trimethylsilyl)-1,1'-bi-2,2'-naphthol ((R)-1) or (S)-3,3'-bis(dimethylphenylsilyl)-1,1'-bi-2,2'-naphthol ((S)-9) depends on the identity of the metal and the nature of the 3,3'-substituents. When M = Be, Zn, or Ge, these amides serve as useful silylation agents that convert only one of the equivalent hydroxyl groups of the binaphthol (R)-1 to a trimethylsilyl ether, whereas the reactions of (R)-1 with the Mg, Ca, or Sn amides generate a polynuclear complex.

Synthesis and structures of an unusual germanium(II) calix[4]arene complex and the first germanium(II) calix[8]arene complex and their reactivity with diiron nonacarbonyl.

The protonolysis reaction of the germanium(II) amide Ge[N(SiMe3)2]2 with calix[4]arene and calix[8]arene furnishes the two germanium(II) calixarene complexes {calix[4]}Ge2 and {calix[8]}Ge4, respectively, which have been crystallographically characterized. The calix[4]arene complex contains a Ge2O2 rhombus at the center of the molecule and is one of the only four germanium(II) calix[4]arenes that have been structurally characterized. The calix[8]arene species is the first reported germanium calix[8]arene complex, and it exhibits an overall bowl-shaped structure which contains two Ge2O2 fragments.

Synthesis of group 1 metal 2,6-diphenylphenoxide complexes [M(OC6H3Ph2-2,6)] (M = Li, Na, K, Rb, Cs) and structures of the solvent-free complexes [Rb(OC6H3Ph2-2,6)]x and [Cs(OC6H3Ph2-2,6)x: one-dimensional extended arrays of metal aryloxides.

Reaction of 2,6-diphenylphenol (HOC(6)H(3)Ph(2)-2,6) with (n)BuLi, NaH, KH, or Rb or Cs metal in benzene gives the solvent-free complexes [M(OAr)]x in excellent yield. The complex [Rb(OC(6)H(3)Ph(2)-2,6)](x)() exhibits a ladderlike structure in the solid state with triply bridging oxygen atoms and Rb-O distances of 2.743(3), 2.