Theoretically predicted divalent silicon(0) compounds: Structures and chemical bonding of silylone in molybdenum pentacarbonyl complexes [Mo(CO)5-Si(XCp∗)2] (X = B–Tl)

Bui

et al. 2020

ACS Omega

Self Cite

Stabilization for tetrylone complexes, which carry ylidone(0) ligands [(CO) 5 W-X (YCp*) 2 ] (X = Ge, Sn, Pb; Y = B–Tl), has become an active theoretical research because of their promising application. Structure, bonding, and quantum properties of the transition-metal donor–acceptor complexes were theoretically investigated at the level of theory BP86 with several types of basis sets including SVP, TZVPP, and TZ2P+. The optimized structures reveal that all ligands X (YCp*) 2 are strongly bonded in tilted modes to the metal fragment W(CO) 5 , and Cp* rings are mainly η 5 -bonded to atom X. DFT-based bonding analysis results in an implication that the stability of W–X bond strength primarily stems from the donation (CO) 5 W ← X(YCp*) 2 formed by both σ- and π-bondings and the electrostatic interaction Δ E elstat . The W–X bond possesses a considerable polarizability toward atom X, and analysis on its hybridization is either sp 2 -characteristic or mainly p-characteristic. EDA-NOCV-based results further imply that the ligands XY perform as significant σ-donors but minor π-donors. The visual simulations of NOCV pairs and the deformation densities assemble a comprehensive summary on different components of the chemical bond via σ- and π-types in the complexes. This work contributes to the literature as an in-depth overview on predicted molecular structures and quantum parameters of the complexes [(CO) 5 W-X(YCp*) 2 ] (X = Ge, Sn, Pb; Y = B–Tl), conducive to either further theoretical reference or extending experimental research.

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“… 1 , 38 The reasoning relates to the existence of the σ-lone-pair orbital leading to the significantly strong σ-orbital interactions. 1 , 31 …”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

In-Depth Investigation of a Donor–Acceptor Interaction on the Heavy-Group-14@Group-13-Diyls in Transition-Metal Tetrylone Complexes: Structure, Bonding, and Property

Bui

et al. 2020

ACS Omega

Self Cite

Structure and property of complexes of group 13 diyl containing subvalent silylone using energy decomposition analysis with natural orbitals for chemical valence

Vietnam Journal of Chemistry

Son

Duc

et al. 2018

Self Cite

The structures and chemical bond in complexes containing subvalent silylone of group 13 diyl W(CO) 5 -Si(XCp*) 2 (W5-SiX) with X = B -Tl using energy decomposition analysis (EDA) method combined with natural orbitals for chemical valence (NOCV) theory have been examined with gradient-corrected DFT at the level BP86/TZ2P+. The calculated equilibrium structures of complexes exhibited that the Si(XCp*) 2 ligands are bonded in a tilted orientation to the metal fragment W(CO) 5 . The EDA-NOCV results indicated that the Si(XCp*) 2 ligands in the complexes are mainly strong and weak π-donors. The trend of the W-Si bond strength resulted from the increase in the ligand-metal donation (CO) 5 WSi(XCp*) 2 . The silylone complexes in this study are suitable targets for synthesis.

Coordination complexes of slight tetrylene with platinum(II)‐8‐hydroxyquinolines: Structure and bonding analysis

Vietnam Journal of Chemistry

Duc

Quy

et al. 2020

The structure and bonding situation in platinum complexes containing slight tetrylene ligands [{PtCl‐C9H6NO}‐NHE] (Pt‐NHE) with E = C, Si, Ge were examined by DFT calculations with the levels are BP86/def2‐SVP and BP86/def2‐TZVPP. The predicted equilibrium structure of the ligands NHE in Pt‐NHE are bonded in distorted end‐on way to PtCl‐8‐hydroxyquinolines fragment with the bending angle, α, exhibits the biggest value in carbenes systems then slightly decrease from Pt‐NHC to Pt‐NHGe. Bond dissociation energies (BDEs), De (kcal.mol‐1), decrease from the carbene complex to the weaker bonded silylene and germylene manners. The BDE when considering dispersion correction at the BP86‐D3(BJ)/def2‐TZVPP level confirms that Pt‐E bond in Pt‐NHE belongs to the effect of the bulky group in slight tetrylene NHE and Pt(II)‐group fragment which makes the intrinsic Pt‐E bond strength decreases from carbene to germylene complexes. The hybridization of atoms E and Pt have large p characters while the hybridization of atom Pt has greater d character which lead to the Pt‐E bond possesses not only NHE→{PtCl‐C9H6NO} strong σ‐donation but also a significant contribution π‐donation NHE→{PtCl‐C9H6NO} and weak π‐backdonation metal‐ligand NHE←{PtCl‐C9H6NO} in complexes Pt‐NHE.