Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation

Vojinovic K, Losehand U, Mitzel NW (2004)
DALTON TRANSACTIONS (16): 2578-2581.

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The crystal structures of (H3C)(2)O, H2SiCl2 and an adduct of these were determined by low-temperature X-ray crystallography on crystals grown in situ at low temperatures on a diffractometer. The adduct of (H3C)(2)O and H2SiCl2 has the composition [(H3C)(2)O.H2SiCl2](2) and contains a four-membered Si2O2 ring, with the Cl atoms pointing to the outside and the Si-H functions pointing to the inner side of the ring. The Si2O2 ring has two longer and two shorter Si...O bonds and thus deviates from a square. Quantum chemical calculations give a geometry for [(H3C)(2)O.H2SiCl2](2) which has D-2h symmetry and allow to obtain an estimate for the adduct formation energies, which are -13.4 kJ mol(-1) for the formation of the mono adduct [(H3C)(2)O + H2SiCl2 --> (H3C)(2)O.H2SiCl2], -14.4 kJ mol(-1) for the dimerization of two mono adducts {(H3C)(2)O.H2SiCl2 --> [((HC)-C-3)(2)O.H2SiCl2](2)} and -41.2 kJ mol(-1) for the reaction 2 (H3C)(2)O + 2 H2SiCl2 --> [(H3C)(2)O.H2SiCl2](2). The results are used to rationalize the strongly reduced reactivity of H2SiCl2 towards nucleophilic substitution reactions in (H3C)(2)O at low temperatures.
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Vojinovic K, Losehand U, Mitzel NW. Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation. DALTON TRANSACTIONS. 2004;(16):2578-2581.
Vojinovic, K., Losehand, U., & Mitzel, N. W. (2004). Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation. DALTON TRANSACTIONS(16), 2578-2581.
Vojinovic, K., Losehand, U., and Mitzel, N. W. (2004). Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation. DALTON TRANSACTIONS, 2578-2581.
Vojinovic, K., Losehand, U., & Mitzel, N.W., 2004. Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation. DALTON TRANSACTIONS, (16), p 2578-2581.
K. Vojinovic, U. Losehand, and N.W. Mitzel, “Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation”, DALTON TRANSACTIONS, 2004, pp. 2578-2581.
Vojinovic, K., Losehand, U., Mitzel, N.W.: Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation. DALTON TRANSACTIONS. 2578-2581 (2004).
Vojinovic, K, Losehand, U, and Mitzel, Norbert W. “Dichlorosilane-dimethyl ether aggregation: a new motif in halosilane adduct formation”. DALTON TRANSACTIONS 16 (2004): 2578-2581.
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CCSD(T)/CBS fragment-based calculations of lattice energy of molecular crystals.
Cervinka C, Fulem M, Ruzicka K., J Chem Phys 144(6), 2016
PMID: 26874495

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