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Theoretical assessment of donor–acceptor complexes [X(PPh3)2 → AlH2]+ (X = C–Pb): structures and bonding

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Abstract

Quantum chemical investigations at the BP86/def2-SVP, BP86/def2-TZVPP and BP86/TZ2P+ levels of theory have been done for the series of AlH2+ complexes that carry carbodiphosphorane and analogues called tetrylones [X(PPh3)2–AlH2]+ (Al-XPPh) (X = C–Pb) using charge and partitioning methods. The most stable structures of Al-XPPh have been found for carbone CPPh as a mildly side-on style in carbone complex Al-CPPh, while the heavier tetrylone adducts Al-SiPPh−Al-PbPPh have significantly different side-on fashions SiPPh−PbPPh, which exhibit the more acute bending angles in tilted forms linked to AlH2+ fragment. Bond dissociation energies (BDEs), De (kcal/mol), slightly decrease from the strongest bonded carbone, Al-CPPh, to the weaker bonded heavier homologues. The bulky tetrylone ligands XPPh have significantly influenced to the Al-X bond strength in complexes Al-XPPh when calculating BDEs with dispersion interaction. The NBO analysis revealed that the [X(PPh3)2 → AlH2]+ donation comes mainly from the σ- and π-contributions of the ligands. The EDA–NOCV calculations showed that the bond sturdiness of the Al–X bond results from the decrease in [X(PPh3)2 → AlH2]+ donation and electrostatic attraction. The EDA–NOCV data also indicated that AlH2+–tetrylone complexes exhibit not only (PPh3)2X → AlH2+ strong σ-donors and weak π-donors but also (PPh3)2X ← AlH2+ weak π-back donation as π–π electrons shared in complexes.

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Acknowledgements

Nguyen Thi Ai Nhung thanks Prof. Dr. Gernot Frenking for allowing the continuous use of her own resources within Frenking’s group. The programs used in the studies were run via the Erwin/Annemarie clusters operated by Reuti (Thomas Reuter) at the Philipps-Universität Marburg, Germany. This research is funded by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under Grant No. 104.06-2017.303 (Nguyen Thi Ai Nhung).

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Authors and Affiliations

  1. Department of Chemistry, University of Sciences, Hue University, Hue City, Vietnam

    Nguyen Thi Ai Nhung, Huynh Thi Phuong Loan & Phung Tan Son

  2. Department of Chemistry, University of Education, Hue University, Hue City, Vietnam

    Hoang Van Duc & Duong Tuan Quang

  3. Faculty of Science and Engineering, Hoa Sen University, Ho Chi Minh City, Vietnam

    Pham Van Tat

  4. Office of Academic Affairs, HCMC University of Food Industry, Ho Chi Minh City, Vietnam

    Dang Tan Hiep

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Nhung, N.T.A., Loan, H.T.P., Son, P.T. et al. Theoretical assessment of donor–acceptor complexes [X(PPh3)2 → AlH2]+ (X = C–Pb): structures and bonding. Theor Chem Acc 138, 67 (2019). https://doi.org/10.1007/s00214-019-2456-8

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