Reactions of Cp*(dmpe)Mo(eta(3)-CH(2)Ph) with organogermanes (RR'GeH(2)) afforded germylene complexes Cp*(dmpe)Mo(H)GeRR' (RR' = Ph(2) (2), Et(2) (3), (Mes)H (4), ((t)Bu)H (5)). Compound 2 does not possess an intramolecular H...Ge interaction of the type exhibited by its silicon analogue and by 3. The existence of such interactions appears to depend on the steric properties of substituents on the Ge (or Si) atom. For comparison, a silylene complex was prepared by reaction of 9-silafluorene with 1, to give Cp*(dmpe)Mo(H)Si(C(12)H(8)), which on the basis of NMR spectroscopy does not possess a significant Si...H interaction.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ic901168s | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Activation of carbon disulfide by a hypersilyl germylene.
Dalton Trans
July 2024
Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune 411008, India.
In this work, the insertion of CS into the Ge-Si bond of PhC(NBu)Ge-Si(SiMe) (1) has been investigated, resulting in the formation of PhC(NBu)Ge-C(S)-S-Si(SiMe) (2). Interestingly, the addition of NHC to 2 allows the release of NHC·CS with concomitant regeneration of 1. Addition of another equivalent of 1 or an analogous hypersilyl silylene, [PhC(NBu)Si-Si(SiMe)], to 2 led to the formation of compounds with a GeS (3) or a SiS (4) bond.
View Article and Find Full Text PDFPolydentate Amidinato-Silylenes, -Germylenes and -Stannylenes.
Chemistry
June 2024
Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, 33071, Oviedo, Spain.
This review article focuses on amidinatotetrylenes that potentially can (or have already shown to) behave as bi- or tridentate ligands because they contain at least one amidinatotetrylene moiety (silylene, germylene or stannylene) and one (or more) additional coordinable fragment(s). Currently, they are being widely used as ligands in coordination chemistry, small molecule activation and catalysis. This review classifies those that have been isolated as transition metal-free compounds into five families that differ in the position(s) of the donor group(s) (D) on the amidinatotetrylene moiety, namely: ED{RNC(R)NR}, EX{DNC(R)NR}, EX{RNC(D)NR}, EX{DNC(R)ND} and E{RNC(R)ND} (E=Si, Ge or Sn).
View Article and Find Full Text PDFFrustrated Lewis pair adducts of alkynyl-capped tetrelenes.
Dalton Trans
April 2024
Department of Chemistry, University of Alberta, 11227 Saskatchewan Dr., Edmonton, Alberta, T6G 2G2, Canada.
The frustrated Lewis pair (FLP) adducts PB{ECl} (PB = PrP(CH)BCy; Cy = cyclohexyl; E = Si, Ge) were used to access a bis(alkynyl)-functionalized silylene and a germylene; the goal behind preparing these species was to obtain new unsaturated main group polymers [E(CCSiMe)] upon heating. While the silylene adduct PB{Si(CCSiMe)} was stable up to 150 °C, the heavier element congener PB{Ge(CCSiMe)} underwent a complicated rearrangement process accompanied by Cy-group migration and Ge(II)-alkyne coordination. Density functional theory computations were performed to understand the mechanistic pathway for the unusual rearrangement of PB{Ge(CCSiMe)}.
View Article and Find Full Text PDFSmall molecule activation by sila/germa boryne species.
J Comput Chem
April 2024
Department of Chemistry, Indian Institute of Technology Madras, Chennai, India.
The inability of p-block elements to participate in π-backbonding restricts them from activating small molecules like CO, H , and so forth. However, the development of the main group metallomimetics became a new pathway, where the main-group elements like boron can bind and activate small molecules like CO and H . The concept of the frustrated Lewis pair, Boron-Boron multiple bonds, and borylene are previously illustrated.
View Article and Find Full Text PDFReactivity of [Cp*Fe(η -As )] towards Carbenes, Silylenes and Germylenes.
Angew Chem Int Ed Engl
January 2024
Institute of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
The reaction behavior of [Cp*Fe(η -As )] (I) (Cp*=C Me ) towards carbenes and their heavier analogs was investigated. The reaction of I with NHCs (NHCs=N-heterocyclic carbenes) results in the first substitution products of polyarsenic ligand complexes by NHCs [Cp*Fe(η -As NHC)] (1 a: NHC=IMe=1,3,4,5-tetramethylimidazolin-2-ylidene, 1 b: NHC=IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene). In contrast, the reaction of I with CAAC ( CAAC=2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene) leads to a fragmentation and the formation of an unprecedented As -sawhorse-type compound [As (As CAAC) ] (2).
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!