A monovalent aluminum monomer [{HC(CMeNAr)2}Al] was obtained by reduction of the corresponding aluminum(III) diiodide. The molecular structure shows a unique two-coordinate center and planar heterocyclic Al-N-C-C-C-N six-membered ring system (see picture). nonbonded lone pair electrons on Al atom indicates Lewis base character center. Ar=2,6-iPr2C6H3.

Stable? You can bottle it! The base-stabilized dichlorosilylene L1SiCl2 (see picture; L1=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) is stable at room temperature. undergo a reaction with diphenylacetylene to form trisilacyclopentene derivative. These compounds have been characterized by X-ray crystallography and computational studies.

Although tetrameric Al(I) compounds have been known for a long time, the monomeric that are analogous to carbenes very recent entrants in chemistry. They possess novel structural features and exhibit distinct reactivity. This has resulted isolation characterization of various unusual aluminum(III) such as aluminatetrazoles aluminacyclopropenes. In comparison emergence aluminum(I) compounds, stable silylenes germylenes (carbene analogues silicon germanium) were recognized much earlier. led...

The single life: reaction of [PhC(NtBu)2]SiCl3 (1) with potassium afforded the monomeric chlorosilylene [PhC(NtBu)2]SiCl (2). X-ray crystal structure 2 has been determined and natural-bond-orbital analysis carried out. Supporting information for this article is available on WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z600647_s.pdf or from author. Please note: publisher not responsible content functionality any supporting supplied by authors. Any queries (other than missing...

Two new approaches for synthesizing RSiCl, (R = PhC(NtBu)2) are reported by the reaction of RSiHCl2 with bis-trimethyl silyl lithium amide and N-heterocyclic carbene respectively. In former method silylene is produced in 90% yield. The was treated biphenyl alkyne to afford disilacyclobutene system. This a rare example two five-coordinate silicon centers arranged adjacent each other four-membered ring. Furthermore, we fluorinated ring trimethyltin fluoride obtain fluoro substituted disilacyclobutene.

A trapped silicon atom: The compound (L:)2Si with low-valent was synthesized from its dichloride biradical precursor (L:)2SiCl2 by reduction KC8. Theoretical analysis suggest that there are two donor–acceptor σ bonds L:→Si←:L. There is one lone-pair orbital at Si and π which features significant π-back-donation L:←Si→:L giving short SiC bonds.

N-Heterocyclic carbenes (NHCs) are known to stabilize some metal atoms in different oxidation states mostly by their strong σ-donation. After the successful syntheses of cyclic alkyl(amino) (cAACs), they have been proven be much more effective stabilizing electron rich species. In cAAC, one σ-withdrawing and π-donating nitrogen NHC is replaced a σ-donating quaternary carbon atom leading lower lying LUMO. This makes acceptance π-back-donation from element bound carbene cAAC energetically...

Isolating stable compounds with low-valent main group elements have long been an attractive research topic, because several of these can mimic transition metals in activating small molecules. In addition, heavier fundamentally different electronic properties when compared their lighter congeners. Among 14 elements, the analogues carbenes (R(2)C:) such as silylenes (R(2)Si:), germylenes (R(2)Ge:), stannylenes (R(2)Sn:), and plumbylenes (R(2)Pb:) are most studied species elements. The first...

The reaction of [LAlH2 ] (L=HC(CMeNAr)2 , Ar=2,6-iPr2 C6 H3 ) with MeOTf (Tf=SO2 CF3 resulted in the formation [LAlH(OTf)] (1) high yield. triflate substituent 1 increases positive charge at aluminum center, which implies that has a strong Lewis acidic character. excellent catalytic activity for hydroboration organic compounds carbonyl groups was investigated. Furthermore, it shown effectively initiates addition trimethylsilyl cyanide (TMSCN) to both aldehydes and ketones. Quantum mechanical...

The well-defined aluminum dihydride LAlH2 (L = HC(CMeNAr)2, Ar 2,6-Et2C6H3) (1) operates in catalysis like a transition metal complex. catalytic activity of 1 for hydroboration terminal alkynes was investigated. Furthermore, catalyst effectively initiated the dehydrocoupling boranes with amines, thiols, and phenols, respectively, to form compounds B-E bonds (E N, S, O) under elimination H2. Quantum mechanical calculations indicate that reactions occur via three consecutive cycloaddition...

A variety of complex inorganic solids with open-framework and other fascinating architectures, involving silicate, phosphate, anions, have been synthesized under hydrothermal conditions. The past few years also seen the successful synthesis characterization several molecular compounds that can act as precursors to form materials, some them resembling secondary building units (SBUs). Transformations rationally materials constitute an important new direction in both structural chemistry enable...

Transition metal compounds are well known as activators of small molecules, and they serve efficient catalysts for a variety homogeneous heterogeneous transformations. In contrast, there is general feeling that main group cannot act because their inability to activate molecules. Traditionally, the activation molecules considered one key steps during catalytic cycle with transition metals. As consequence, researchers have long neglected full range possibilities in harnessing elements design...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMolecular Phosphonate Cages: Model Compounds and Starting Materials for Phosphate Materials‡Mrinalini G. Walawalkar, Herbert W. Roesky, Ramaswamy MurugavelView Author Information Institute of Inorganic Chemistry, University Göttingen, Tammannstrasse 4, D-37077 Germany Chemistry Department, Indian Technology, Powai, Bombay-400 076, India Cite this: Acc. Chem. Res. 1999, 32, 2, 117–126Publication Date (Web):November 21, 1998Publication History...

Reaction of the β-diketiminato lithium salt Li(OEt2)[HC(CMeNAr)2] (Ar = 2,6-i-Pr2C6H3) with GeCl2·(dioxane) and SnCl2 in diethyl ether provided monomeric complexes [HC(CMeNAr)2]MCl (M Ge (2), Sn (3), respectively) a three-coordinated metal center. The reductive dehalogenation reactions 3 C8K LiAlH4 afforded [HC(CMeNAr)2]2Sn (7) [HC(CMeNAr)2]AlH2, respectively. metathesis t-BuLi, AgSO3CF3, NaN3 resulted formation [HC(CMeNAr)2]Sn(t-Bu) (4), [HC(CMeNAr)2]Sn(OSO2CF3) (5), [HC(CMeNAr)2]SnN3 (6),...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDiscrete Silanetriols: Building Blocks for Three-Dimensional MetallasiloxanesRamaswamy Murugavel, Vadapalli Chandrasekhar, and Herbert W. RoeskyView Author Information Institut für Anorganische Chemie, Tammannstrasse 4, D-37077 Göttingen, GermanyCite this: Acc. Chem. Res. 1996, 29, 183–189Publication Date (Web):April 11, 1996Publication History Received9 August 1995Published online11 April 1996Published inissue 11...

Al4Se4 and Al4Te4 cubes are the central structural units of heterocubanes [(Cp*AlSe)4] [(Cp*AlTe)4] 1 (structure shown on right). These compounds were formed by reaction tetrameric AlI compound [(Cp*Al)4] with elemental selenium tellurium, respectively. The driving force this smooth is conversion from to AlIII. Cp* = η5-C5Me5

Recent years have witnessed important developments in organosilicon chemistry, courtesy to the high yield access of stable monomeric chlorosilylene (LSiCl, L = PhC(NtBu)2) and N-heterocyclic carbene (NHC) stabilized dichlorosilylene (L1SiCl2, L1 1,3-bis(2,6-iPr2C6H3)imidazol-2-ylidene) by dehydrochlorination technique using strong bases such as carbenes or LiN(SiMe3)2 HCl scavenger. The chemistry functionalized silylenes is markedly different from previously reported dicoordinate silylenes....

This article reports the reduction of chloride [PhC(NtBu)2]GeCl with potassium in THF to afford reddish crystals [PhC(NtBu)2]2Ge2 (2). The molecule 2 contains a Ge−Ge bond. X-ray structure and DFT calculation indicate that bond possesses an unusual gauche-bent geometry. length is 2.570 Å, which very close single interaction (2.61 Å) but significantly longer than for typical digermenes, R2GeGeR2 (2.21−2.51 two structurally characterized digermynes (2.2850 Å 2.2060 Å), proves there no multiple...

The cyclic alkyl(amino) carbene (cAAC:)-stabilized acyclic germylones (Me2-cAAC:)2Ge (1) and (Cy2-cAAC:)2Ge (2) were prepared utilizing a one-pot synthesis of GeCl2(dioxane), cAAC:, KC8 in 1:2:2.1 molar ratio. Dark green crystals compounds 1 2 produced 75 70% yields, respectively. reported methods for the preparation corresponding silicon turned out to be not applicable case germanium. single-crystal X-ray structures feature C-Ge-C bent backbone, which possesses three-center two-electron...

The reaction of L'Si [L' = CH{(C=CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}] with ammonia under oxidative addition results in L'Si(H)NH(2). H(3)NBH(3) functions as a source hydrogen for the hydrogenation N-heterocyclic carbenes and germylenes.