Weak Arene Stabilization of Bulky Amido‐Germanium(II) and Tin(II) Monocations

Li, Jiaye; Schenk, Christian; Winter, Florian; Scherer, Harald; Trapp, Nils; Higelin, Alexander; Keller, Sarah; Pöttgen, Rainer; Krossing, Ingo; Jones, Cameron

doi:10.1002/anie.201204601

Cited by 108 publications

(100 citation statements)

References 46 publications

(24 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…None of the charge calculations clearly conclude about the ionocity of these cations and given by their high-field shifts especially in 29 Si and 119 Sn NMR, one would expect that the charges are not completely residing on the central atom. 70 Recently, the group of Stalke extensively studied the charge density of various low valent silicon compounds 96 like 1,4disilabenzene, 97 hexasilabenzene 98 etc. Perhaps experimental charge density studies of few of these cations would bring more clear pictures of their bonding situation.…”

Section: Discussionmentioning

confidence: 99%

“…Again when 3 was dissolved in solvents, a colorless solution of 2 was obtained. This unusual behavior could be rationalized by steric strain in the solid 70 disilene, flexibility in bonding modes of Cp* groups, low activation energy for the equilibrium process, small energy difference between 2 and 3. It should be noted here that dehydrochlorination of [(η 1 -Me 5 C 5 )SiHCl 2 ] with KN(SiMe 3 ) 2 also led to disilene 3 in higher yield.…”

Section: Methodsmentioning

confidence: 99%

“…A chelating bis(iminophosphorane)ligand has been recently 70 used by Driess et al to obtain a chlorosilyliumylidene complex 12 through ligand exchange of the SiCl 2 unit. 54 NHC·SiCl 2 18a was used as a stoichiometric source of SiCl 2 and its reaction with bis(iminophosphorane) ligand resulted in the ion pair with concomitant liberation of one equivalent NHC (Scheme 8).…”

Section: Donor Stabilized Si(ii) Cationmentioning

confidence: 99%

“…17 The concept of donor-stabilization has recently been used for the isolation of a series of highly reactive compounds which were otherwise inaccessible. For example, the 70 groups of Roesky and Filippou showed that the reactivity of silylenes like SiCl 2 or SiBr 2 can be tamed when they are attached to a N-heterocyclic carbene. 18 The N-donor stabilized amidinato chlorosilylene [PhC(NtBu) 2 SiCl] from the Roesky group, also enjoyed substantial attention in recent years.…”

Section: Introductionmentioning

confidence: 99%

“…The groups of Alcarazo and Vidovic used a divalent C(0) compound, commonly known as carbodiphosphorane [(PPh 3 ) 2 C], for the realization of B, 30a Ge, 30b and P 31 centered cations. The main advantage of these C(0) 70 ligands over NHCs is that they are capable of acting as σ-as well as π-donors. A recent computational paper by Toner and Frenking proposed that the substitution of an NHC by a carbodiphosphorane in the Grubbs' catalyst for alkene metathesis might lead to an enhanced reactivity.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Cations and dications of heavier group 14 elements in low oxidation states

et al. 2015

View full text Add to dashboard Cite

Cations and dications of heavier group 14 elements in their low oxidation state have received widespread attention in recent years. The journey started with the isolation of a series of cations of the composition [(C5Me5)E:](+) [E = Si-Pb], followed by the more recent isolation of a Ge(ii) dication encapsulated within a cryptand, a carbodiphosphorane stabilized [GeCl](+) monocation with a two coordinate Ge atom, Si(ii) cations and dications stabilized by N-heterocyclic carbenes (NHCs), which highlights the ongoing growth and interest in the chemistry of tetrel(ii) cations. This is presumably because the central atom (E) in these compounds contains two or three unoccupied valence orbitals as well as holds a lone pair of electrons. Such an electronic description represents ambiphilicity, which is of great interest for catalysis. The successful synthesis of divalent group 14 cations requires new synthetic strategies based on the sterically demanding neutral or monoanionic ligands, utilization of counter anions, and solvents with low nucleophilicity in order to minimize the degree of interactions with the cations. An alternative approach for the realization of divalent cations of group 14 elements is their coordination to the transition metals. This synthetic approach was successfully applied for the isolation of a range of transition metal coordinated divalent cations of group 14 elements. Apart from arousing academic interest some of these cations have found application as activators in the Ziegler-Natta polymerization of alkenes.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Donor Stabilized Si(ii) Cationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Cations and dications of heavier group 14 elements in low oxidation states

et al. 2015

View full text Add to dashboard Cite

show abstract

X‐ray Crystallography of Organogermanium Compounds

Hemmert¹

2023

Organogermanium Compounds

View full text Add to dashboard Cite

Recent Advances in the Chemistry of Germanium(II) Cationic Compounds

Mukherjee,

Khan,

Haldar

et al. 2023

Encyclopedia of Inorganic and Bioinorganic Chemistry

View full text Add to dashboard Cite

The syntheses and stabilizations of germanium(II) cationic compounds have been known for long. Contemporary research have been engaged in tailoring the germanium(II) cationic species for applications in small‐molecule activation and catalysis. This article comprises the discussion on the three major types of germanium(II) cationic compounds: (1) germanium(II) monocation or germyliumylidene, (2) bis(germyliumylidene), and (3) germanium(II) dication. Herein, earlier reports on the stabilization of germanium(II) mono‐ and dications have been briefly mentioned. The article includes the latest findings on the stabilization of the germanium(II) cationic species. The major focus of the article has been on discussing how the choice of the supporting ligands becomes the determining factor for tuning the frontier electronics and hence the applicability of the cationic germanium(II) compounds. Examples of bond activation at the ambiphilic germanium(II) monocationic sites and their catalytic applications, element–ligand cooperative bond activations, transition metal‐main group cooperative catalysis, reverse polarization at the germanium(II) cationic site, cooperative interactions between two germanium(II) cationic sites, leading to organic transformations, etc., which are some of the remarkable findings, have been discussed. This overview on the advancements made in this field will provide a background knowledge for further explorations.

show abstract

Weak Arene Stabilization of Bulky Amido‐Germanium(II) and Tin(II) Monocations

Cited by 108 publications

References 46 publications

Cations and dications of heavier group 14 elements in low oxidation states

Cations and dications of heavier group 14 elements in low oxidation states

X‐ray Crystallography of Organogermanium Compounds

Recent Advances in the Chemistry of Germanium(II) Cationic Compounds

Contact Info

Product

Resources

About