Photoelectron spectroscopy combined with quantum chemistry has been a powerful approach to elucidate the structures and bonding of size-selected boron clusters (B n − ), revealing a prevalent planar world that laid the foundation for borophenes. Investigations of metal-doped boron clusters not only lead to novel structures but also provide important information about the metal-boron bonds that are critical to understanding the properties of boride materials. The current review focuses on recent advances in transition-metal-doped boron clusters, including the discoveries of metal-boron multiple bonds and metal-doped novel aromatic boron clusters. The study of the RhB − and RhB 2 O − clusters led to the discovery of the first quadruple bond between boron and a transition-metal atom, whereas a metal-boron triplebond was found in ReB 2 O − and IrB 2 O − . The ReB 4 − cluster was shown to be the first metallaborocycle with Möbius aromaticity, and the planar ReB 6 − cluster was found to exhibit aromaticity analogous to metallabenzenes. 

Probing the Nature of the Transition-Metal-Boron Bonds and Novel Aromaticity in Small Metal-Doped Boron Clusters Using Photoelectron Spectroscopy

Although the toxicity of beryllium compounds causes impediments in experiments involving them, beryllium chemistry has seen a recent upsurge of interest and considerable progress. Computations play a very important complementary role in analyzing the structure, stability and bonding of these compounds. In this perspective article, we highlighted our contribution to beryllium chemistry which is either completely through theoretical results or sometimes supported by experimental findings. It starts with the smallest 2π aromatic system, Be32-, which also exhibits rare bond-stretch isomerism. Furthermore, its reactivity towards different transformations is mentioned. Because of the ability of beryllium to attain a high ionic potential, the beryllium center in an appropriate situation can act as an excellent Lewis acid which is utilized to bind noble gas (Ng) atoms, carbon monoxide and dinitrogen through donor-acceptor types of interactions. We made several efforts to have strong Ng-Be bonds which led us to NgBeNCN that is recorded to have the strongest Ng-Be bond among the neutral Ng-Be complexes reported so far. Significant dinitrogen activation was also achieved in (NN)2Be(η2-N2) and OCBeNN complexes. In the latter case, a complete cleavage of the N-N bond producing the most stable NBeNCO molecule has occurred. We also found viable M2(NHBMe)2 (M = Be, Mg) complexes having unusual bonding where the interacting fragments are best described as the neutral M2 and (NHBMe)2 but M2 still possesses a single bond. We finally discussed the complex comprising an unusual Be(i) oxidation state, [BeI(cAACAr)2]+˙ and di-ortho-beryllated carbodiphosphorane exhibiting Be⇇C double dative bonds.

Intriguing structural, bonding and reactivity features in some beryllium containing complexes

We report the chemical bonding and reactivity of the first example of neutral 18 valence electron transition metal complexes of beryllium, [BeM(CO)4; M = Fe - Os], in trigonal bipyramidal coordination geometry, where the bonding between the transition metal and the s-block element beryllium (M-Be) can be best described by dative quadruple bonds. In contrast to the conventional multiple bonding pattern, the quadruple bonds comprise two σ-bonds and two π-bonds, viz., one Be → M σ-bond, one M → Be σ-bond, and two M → Be π-bonds. Since the M-Be quadruple bonds are described by dative interactions, the Be centre shows ambiphilic character as indicated by the high proton and hydride affinity values.

Two σ- and two π-dative quadruple bonds between the s-block element and transition metal in [BeM(CO)4; M = Fe - Os].

Carbodicarbene (CDC) has become an emerging ligand in many fields due to their strong σ-donating ability. We report the synthesis of the first anionic CDC pincer Pd complexes containing a BF2 moiety within the framework, a charge-frustration zwitterion approach to leverage the electronic feature of carbon(0)/carbone, which is unprecedented. The elucidation of X-ray crystal structures, ligand competition as well as transmetallation experiments suggest that the anionic moiety has enhanced the overall donor strength of the traditional neutral CDC. Importantly, this anionic scaffold exhibits a facile second coordination toward Au(I), Ag(I) and Pd(II) without any external ligand assistance, whereas previously reported neutral pincer CDC complexes do not possess a two-fold donor capacity. The analysis of the bonding situation via theoretical methods shows that the description of the anionic CDC moieties in terms of dative bonding is preferred over the model of delocalized positive charge, as it accounts for the two-fold donor ability of the divalent carbon atom, preserving characteristic feature of a carbone.

Diversification of Carbodicarbene Class by Embedding an Anionic Component in its Scaffold.

The recent report of planar tetracoordinate hydrogen (ptH) in In 

InnTl4–nH+ (n = 0∼4): Tetracoordinate Hydrogen in a Planar Fashion?

Density functional theory calculations at the M06-D3/def2-TZVPPD level of the group-13 anion complexes EFe(CO)3- (E = B-Tl) and the isoelectronic neutral and charged boron adducts BTM(CO)3q (TMq = Fe-, Ru-, Os-, Co, Rh, Ir, Ni+, Pd+, Pt+) give tetrahedral (C3v) geometries in the 1A1 electronic ground state as equilibrium structures. The analysis of the bonding situation with the energy decomposition analysis in combination with natural orbital for chemical valence method suggests that the E-TM(CO)3q bonds possess four bonding components: (a) one strong electron-sharing σ bond E-TM(CO)3q; (b) two π backdonations E⇇TM(CO)3q and (c) one weak σ donation E→TM(CO)3q. The relative strength of the four bonding components depends on the charge of the system, the transition metal TM and the group-13 atom E. The σ donation E→TM(CO)3q is in all systems rather weak while the associated charge migration is not negligible. A similar situation of the bonding of terminal group-13 atoms Ga and In is found in Ga-TM(GaCp)4+ and E-Pt(PMe3)3+ (TM = Ni, Pd, Pt; E = Ga, In), which are model compounds for the stable complexes GaTM(GaCp*)4+ (TM = Ni, Pt) and InPt(PPh3)3+. The quadruple bonds E→TML2 are hybrids of electron-sharing and dative bonds.

Quadruple bonding of bare group-13 atoms in transition metal complexes.

Handle everyday research tasks with reliable, citation-backed results

Your personal Research Agent to handle research tasks with citation-backed results

Popular Tasks used by Researchers

How can I help with your research?

Meet SciSpace

Get more enhanced response by uploading the PDFs you want me to reference.

No relevant PDFs in your library

SciSpace is the AI research assistant for academics. Run systematic literature reviews on 280M+ papers, and write papers with cited sources. Trusted by 1M+ students, PhDs & researchers.

SciSpace | AI for Research

Analyze PDFs

Code & Manuscripts

Funding & Grants

Literature & Patents

Medical & Clinical Data

Systematic Review

Visualize & Present

Web & Data

Build a Google Scholar-like website for your research.

Build a website

Create charts and images for your research

Create a Chart

Write a paper for submission to a journal

Draft a manuscript

Patent Search

Design eye-catching scientific posters in minutes.

Scientific Poster Generation

Systematic Literature Review

One task is running at the moment. Your messages will be shown right after.

Drag and drop or click here to browse

Loved by <highlight>1 million+</highlight> researchers

Extract a list of specific topics and their sources from unstructured text

Topics

Compare and analyze relevant papers that matches with your search

Papers

Get insights from PDFs and bookmarked papers from your library

My library

Recent searches

Try searching for:

Catch AI-generated content in scholarly and non-scholarly content

{ai} Detector

Ai Writer

Get PDF Summaries, highlighted text explanations 

Chat with PDF

Effortlessly create in-text citations and bibliographies in APA and 2,500 other formats

Citation generator

Get explanations, summaries, and answers on academic papers

Ease up your research workflow with {scispace}'s cohort of exciting AI tools

Elevate your academic writing skills and convey your ideas the way you want

Paraphraser

Explore our range of reading and writing tools

Your file is being prepared and should be ready in a few minutes. If it's a large file, it might take a bit longer. You can close this window, and we'll email you the file when it's done.

You have reached a maximum limit of {limit} columns in the table. Remove at least 1 column to add or create another one.

Sai Manoj

Author Tools

Chat about Author

Papers

Quadruple bonding of bare group-13 atoms in transition metal complexes.