Herein, we report the employment of the Mo-Mo quintuple bonded amidinate complex to stabilize Group 10 metal fragments {(Et3P)2M} (M=Pd, Pt) and give rise to the isolation of the unprecedented δ complexes. X-ray analysis unambiguously revealed short contacts between Pd or Pt and two Mo atoms and a slight elongation of the Mo-Mo quintuple bond in these two compounds. Computational studies show donation of the Mo-Mo quintuple-bond δ electrons to an empty σ orbital on Pd or Pt, and back-donation from a filled Pd or Pt dπ orbital into the Mo-Mo δ* level (LUMO), consistent with the Dewar-Chatt-Duncanson model.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.201504414 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Analysis of chemical bonding of the ground and low-lying states of Mo and of MoCl complexes, x = 2-10.
J Chem Phys
August 2022
Laboratory of Physical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, Athens 157 84, Greece.
In this study, we perform accurate calculations via multireference configuration interaction and coupled cluster methodologies on the dimolybdenum molecule in conjunction with complete series of correlation and weighted core correlation consistent basis sets up to quintuple size. The bonding, the dissociation energies, and the spectroscopic parameters of the seven states that correlate with the ground state products are calculated. The ground state has a sextuple chemical bond, and each of the calculated excited states has one less bond than the previous state.
View Article and Find Full Text PDFMo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.
Inorg Chem
April 2017
Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan.
The recently reported high reactivity of the Mo-Mo quintuple bond of Mo(NN) (1) {NN = μ-κ-CH[N(2,6-iPrCH)]} in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° = 9.
View Article and Find Full Text PDFThe Mo-Mo Quintuple Bond as a Ligand to Stabilize Transition-Metal Complexes.
Angew Chem Int Ed Engl
July 2015
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences and Matters, National Tsing Hua University, 101, Sec. 2, Guang-Fu Road, Hsinchu 300 (Taiwan).
Herein, we report the employment of the Mo-Mo quintuple bonded amidinate complex to stabilize Group 10 metal fragments {(Et3P)2M} (M=Pd, Pt) and give rise to the isolation of the unprecedented δ complexes. X-ray analysis unambiguously revealed short contacts between Pd or Pt and two Mo atoms and a slight elongation of the Mo-Mo quintuple bond in these two compounds. Computational studies show donation of the Mo-Mo quintuple-bond δ electrons to an empty σ orbital on Pd or Pt, and back-donation from a filled Pd or Pt dπ orbital into the Mo-Mo δ* level (LUMO), consistent with the Dewar-Chatt-Duncanson model.
View Article and Find Full Text PDFThe important role of the Mo-Mo quintuple bond in catalytic synthesis of benzene from alkynes. A theoretical study.
Dalton Trans
August 2014
Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan.
The Mo-Mo quintuple bond was recently applied to catalytic synthesis of benzene from alkynes, which is the first example of the catalytic reaction of the metal-metal multiple bond. This new reaction was studied using DFT and CASSCF/CASPT2 methods. The entire catalytic cycle consists of four steps: [2 + 2], [4 + 2], and [6 + 2] cycloadditions, and reductive elimination of benzene.
View Article and Find Full Text PDFAn electron-rich molybdenum-molybdenum quintuple bond spanned by one lithium atom.
Angew Chem Int Ed Engl
June 2012
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013, Taiwan.
Take five: A unique quintuply bonded dimolybdenum complex [Mo(2)(μ-Li){μ-HC(N-2,6-Et(2)C(6)H(3))(2)}(3)] (see picture) was synthesized and characterized. The Mo-Mo interaction includes an unexpected bridging Li(+) ion. Calculations indicate the bridging Li(+) ion does not perturb the Mo-Mo bond length (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!