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Theoretical exploitation of donor‐acceptor ability in low‐valent group‐14 elements complexes [E(PPh 3 ) 2 → SiH 2 ] 2+ (E = C to Pb) using energy decomposition analysis
Author(s) -
Loan Huynh Thi Phuong,
Van Duc Hoang,
Quang Duong Tuan,
Cong Vo Thanh,
Van Tat Pham,
Trung Nguyen Tien,
Nhung Nguyen Thi Ai
Publication year - 2019
Publication title -
vietnam journal of chemistry
Language(s) - English
Resource type - Journals
eISSN - 2572-8288
pISSN - 0866-7144
DOI - 10.1002/vjch.201900078
Subject(s) - chemistry , dissociation (chemistry) , acceptor , crystallography , electronic structure , bond dissociation energy , electron capture dissociation , computational chemistry , ion , physics , organic chemistry , condensed matter physics , fourier transform ion cyclotron resonance
The structure and bonding of complexes containing subvalent group‐14 elements [E(PPh 3 ) 2 → SiH 2 ] 2+ ( Si‐EP ) with E = C to Pb have been researched using charge‐ and EDA‐NOCV methods. The optimized equilibrium geometries for complexes have the most stable structure which has been found for carbone ligand CP as the nearly end‐on bonded form in Si‐CP . In contrast to this, the heavier ligands SiP to PbP in the heavier complexes Si‐SiP to Si‐PbP exhibit strongly side‐on manners. Bond dissociation energies, ‐ D e (kcal.mol ‐1 ), increase from Si‐CP to the stronger bonded complexes Si‐SiP to Si‐PbP . EDA‐NOCV calculations revealed that the donation [E(PPh 3 ) 2 → SiH 2 ] 2+ displays the significant σ‐interactions of the ligands while the π‐electron sharing exhibits the charges transfer between E(PPh 3 ) 2 and SiH 2 2+ . Bonding analysis indicated that the Si‐E bond results from the decrease in the donation [E(PPh 3 ) 2 → SiH 2 ] 2+ and electrostatic attraction. The investigated complexes possessed E(PPh 3 ) 2 → SiH 2 2+ strong σ‐donors and E(PPh 3 ) 2 ↔ SiH 2 2+ π‐π electrons shared between the two fragments.