Cations and dications of heavier group 14 elements in their low oxidation state have received widespread attention recent years. The journey started with the isolation a series cations composition [(C5Me5)E:](+) [E = Si-Pb], followed by more Ge(ii) dication encapsulated within cryptand, carbodiphosphorane stabilized [GeCl](+) monocation two coordinate Ge atom, Si(ii) N-heterocyclic carbenes (NHCs), which highlights ongoing growth interest chemistry tetrel(ii) cations. This is presumably...

Abstract Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species that serve as valuable building blocks for complex molecules but tend to isomerize cyclize therefore difficult isolate. Using a mild ligand exchange reaction at the carbon in α‐metalated ylides, we have now succeeded synthesis gram‐scale isolation of elusive cyanoketenyl anion [NC 3 O] − . Despite its assumed cumulene‐like structure delocalization negative charge across whole...

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized the preparation PhC(NtBu)2Si{Si(SiMe3)3} (1) from PhC(NtBu)2SiHCl2 K{Si(SiMe3)3} in more than 90% yield. The highly deshielded 29Si NMR resonance (δ = 76.91 ppm) can be attributed to absence π-donating substituent. molecular structure 1 shows trigonal-planar geometry around SiII center SiII-SiIV bond length 2.4339(13) Å. A series reactions Me3NO, S, Se, and Te were performed. While siloxane...

This study demonstrates the first example of use a penta-coordinate Si(<sc>iv</sc>) hydride (PhC(N<italic>t</italic>Bu)₂SiH(CH₃)Cl) as catalyst for cyanosilylation variety aldehydes under mild conditions.

Silylene [PhC(NtBu)2SiN(SiMe3)2] (1) cleaves the C(sp3)-H and C-F bonds of acetophenone 1,1,1-trifluoroacetophenone, respectively, under mild conditions. The reaction is initiated via a nucleophilic attack from oxygen to silicon atom followed by C-F/H bond cleavage. scope activation has further been extended with C6F6 C6F5CF3.

The recently reported hypersilylsilylene PhC(NtBu)2SiSi(SiMe3)3 (1) reacts with BH3, 9-BBN, and PhBCl2 to yield the respective Lewis acid base adducts 2–4, respectively. Compound 4 undergoes isomerization form a ring expansion product 5. same silylene was found initially an adduct HBpin (6) subsequently isomerized 7 via rupture of B–H bond (7), where hydride bound carbon atom amidinate ligand Bpin unit attached silicon center. Surprisingly, reaction 1 HBcat results in PhC(NtBu)2Bcat (8)....

Silylene mediated B–H and aldehyde C–H bond splitting were realized under ambient conditions.

Herein, we introduce isocyanide as a ligand in main group chemistry and describe the facile isolation of Ge(ii) dication. The reaction 2,6-dimethylphenylisocyanide with GeCl2 leads to formation dication two [GeCl3](-) molecules counter anions. dicationic center is bound four ligands also holds lone pair electrons. DFT calculations reveal that stabilized only by σ-donation from ligands. Natural population analysis gives charge +0.74 on center, indicating positive shared substituents.

Abstract Soluble calcium halides reported so far are mostly dimeric in nature. The occupy the bridging position and thus provide additional coordination to metal. We obtained a monomeric iodide [{PhC(N i Pr) 2 }CaI(thf) 3 ] ( 1 ) from reaction of [PhC(N ]Li with CaI THF. compound has been stabilized by electronic donation steric shielding amidinate ligand as well three THF molecules. does not show any propensity towards exchange reaction. When same is carried out diethyl ether instead THF,...

The scope of a pendant picolyl group in the β-diketiminate system is explored, which gives rise to diverse germylenes and six-membered dialane, analogous cyclohexane.

The synthesis and structure analysis of a series mono diylide-substituted tetrylenes type YEX Y2 E (E=Ge, Sn, Pb; X=Cl or Br) using thiophosphinoyl-tethered metallated ylide (Y=Ph2 P(S)-C-P(pip)Ph2 with pip=piperidyl) is reported, amongst the first ylide-substituted plumbylenes. feature distinct trends in spectroscopic structural properties ligand increasing atomic number tetrel element. For instance, an increasingly high-field shifted signal for thiophosphinoyl group observed 31 P{1 H} NMR...

Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species, that serve as valuable building blocks to complex molecules but tend isomerize cyclize therefore difficult isolate. Until date, numerous (hetero)cumulenes have been detected in the interstellar medium assumed be important intermediates prebiotic chemistry, particular when containing nitrogen oxygen functionalities. Using a mild ligand exchange reaction at carbon metalated ylides, we now...

Abstract Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species that serve as valuable building blocks for complex molecules but tend to isomerize cyclize therefore difficult isolate. Using a mild ligand exchange reaction at the carbon in α‐metalated ylides, we have now succeeded synthesis gram‐scale isolation of elusive cyanoketenyl anion [NC 3 O] − . Despite its assumed cumulene‐like structure delocalization negative charge across whole...

Abstract Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, series ferrocenyl diphosphines functionalized with no, one or two moieties and corresponding bimetallic complexes were prepared. The feature an anti‐conformation phosphine moieties, guaranteeing presence independent metal centers. Comparative studies in hydroamination...

Abstract The synthesis of two stable monoylide‐substituted stannylenes type Y CN SnR [R=Cl ( 1 ) or N(SiMe 3 2 ), and =Ph P(CN)C] starting from the cyanido‐substituted α‐metallated ylide – K SnCl (SiMe NSnCl is reported. Coordination cyano group to tin center results in dimerization both solid state as well solution, where syn ‐ anti ‐isomers are present. X‐ray diffraction analyses combination with DFT calculations revealed that π‐electron density ligand predominantly shifted into moiety...

The present work focuses on the reactivity of S,S-bis-ylide 2, which presents a strong nucleophilic character, as evidenced by reactions with methyl iodide and CO2, affording C-methylated salts 3 betaine 4, respectively. derivatization 4 affords corresponding ester derivative 6, is fully characterized using NMR spectroscopy X-ray diffraction analysis. Furthermore, an original reaction phosphenium ions leads to formation transient push–pull phosphino(sulfonio)carbene 8, rearranges give...

Abstract Review: 146 refs.

Owing to the strong electron-donating ability of ylide substituents, diylidyltetrylenes are usually highly nucleophilic species with donor capacities. Here, we demonstrate that their electronic properties in fact flexible and can be effectively tuned through variation substituent backbone. Initial density functional theory studies showed cyano groups particularly capable lowering LUMO energy diylidyl germylenes thus turning these into electrophilic compounds. This was confirmed by...