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Experimental and quantum-chemical study of complexation of carbene analogs with dinitrogen. Direct IR-spectroscopic observation of Cl2Si·N2 complexes in low-temperature argon-nitrogen matrices

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Abstract

Interaction of dichlorosilylene with dinitrogen in mixed Ar—N2 matrices at 9 - 10 K was studied by IR spectroscopy. A donor-acceptor complex Cl2Si·N2 was found and characterized by six bands of symmetric (at 511.2, 508.9, and 506.5 cm–1) and antisymmetric (at 500.1, 496.9, and 495.1 cm–1) stretching vibrations of Si—Cl bonds in the most abundant isotopomers. Two bands at 498.7 and 493.5 cm–1 observed in mixed matrices were tentatively assigned to Cl2Si·(N2)2 complex. Several stretching vibration bands of minor isotopomers of SiCl2 were detected for the first time in argon matrices. Assignment has been done for the isotopic structure of SiCl2 associates with dinitrogen observed in N2 matrices. Dimerization of SiCl2 and its complexation with one and two N2 molecules were studied by quantum-chemical DFT calculations (PBE and B3LYP functionals). The structures, energies, and vibrational frequencies of the Cl2Si·N2 and Cl2Si·(N2)2 complexes and the Si2Cl4 dimer were determined. The energies of SiCl2 complexation with one and two N2 molecules obtained from PBE and B3LYP calculations are 0.3 and 0.6 kcal mol–1, respectively. More accurate G2(MP2,SVP) calculations using the B3LYP geometries have predicted a higher stability of the Cl2Si·N2 complex (1.2 kcal mol–1). The calculated and experimental vibrational frequencies of reagents and complexes are in good agreement. A correlation has been established between the PBE calculated energies of complexation of EHal2 (E = Si, Ge, Sn, Pb) with N2 and the experimentally observed shifts of E—Hal stretching vibrations in EHal2 upon complexation. The strength of the complexes with N2 increases on going from dihalosilylenes to dihaloplumbylenes.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    A. V. Lalov, S. E. Boganov, V. I. Faustov, M. P. Egorov & O. M. Nefedov

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  1. A. V. Lalov
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  2. S. E. Boganov
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  3. V. I. Faustov
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  4. M. P. Egorov
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  5. O. M. Nefedov
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Lalov, A.V., Boganov, S.E., Faustov, V.I. et al. Experimental and quantum-chemical study of complexation of carbene analogs with dinitrogen. Direct IR-spectroscopic observation of Cl2Si·N2 complexes in low-temperature argon-nitrogen matrices. Russian Chemical Bulletin 52, 526–538 (2003). https://doi.org/10.1023/A:1023973815486

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