Fascinating transformations of donor-acceptor complexes of group 13 metal (Al, Ga, In) derivatives with nitriles and isonitriles: from monomeric cyanides to rings and cages.
Formation of the donor-acceptor complexes of group 13 metal derivatives with nitriles and isonitriles X(3)M-D (M = Al,Ga,In; X = H,Cl,CH(3); D = RCN, RNC; R = H,CH(3)) and their subsequent reactions have been theoretically studied at the B3LYP/pVDZ level of theory. Although complexation with MX(3) stabilizes the isocyanide due to the stronger M-C donor-acceptor bond, this stabilization (20 kJ mol(-1) at most) is not sufficient to make the isocyanide form more favorable. Relationships between the dissociation enthalpy DeltaH degrees (298)(diss), charge-transfer q(CT), donor-acceptor bond energy E(DA), and the shift of the vibrational stretching mode of the CN group upon coordination Deltaomega(CN) have been examined. For a given metal center, there is a good correlation between the energy of the donor-acceptor bond and the degree of a charge transfer. Prediction of the DeltaH degrees (298)(diss) on the basis of the shift of CN stretching mode is possible within limited series of cyanide complexes (for the fixed M,R); in contrast, complexes of the isocyanides exhibit very poor Deltaomega(CN) - DeltaH degrees (298)(diss) correlation. Subsequent X ligand transfer and RX elimination reactions yielding monomeric (including donor-acceptor stabilized) and variety of oligomeric cage and ring compounds with [MN]n, [MC]n, [MNC]n cores have been considered and corresponding to thermodynamic characteristics have been obtained for the first time. Monomeric aluminum isocyanides X(2)AlNC are more stable compared to Al-C bonded isomers; for gallium and indium situation is reversed, in qualitative agreement with Pearson's HSAB concept. Substitution of X by CN in MX(3) increases the dissociation enthalpy of the MX(2)CN-NH(3) complex compared to that for MX(3)-NH(3), irrespective of the substituent X. Mechanisms of the initial reaction of the X transfer have been studied for the case X = R = H. The process of hydrogen transfer from the metal to the carbon atom in H(3)M-CNH is thermodynamically favorable and is likely to be intramolecular. By contrast, intramolecular hydrogen transfer in H(3)M-NCH has been definitely ruled out. Head-to-tail dimeric species [H(3)M-(NC)H](2) are formed exothermically and exhibit low H.H distances, which can assist in hydrogen transfer, and are likely to be the starting point for H(2) elimination. Elimination of H(2), CH(4), and C(2)H(6) from X(3)M-(NC)R adducts is very favorable thermodynamically; by contrast, elimination of HCl and CH(3)Cl is highly unfavorable even if formation of oligomer species takes place. Thus, high-temperature generation of gas-phase rings and clusters has been predicted viable in the cases X = H,CH(3) and their presence in the reactor media should not be neglected. Moderate stability of [HMCH(2)NH](4) clusters (especially in the cases M = Ga, In) makes these species viable intermediates of gas-phase reactions. Their formation may be responsible for the carbon contamination in the course of metal organic chemical vapor deposition processes of group 13 binary nitrides.
Timoshkin
Alexey Y
AY
Department of Chemistry, Inorganic Chemistry Group, St. Petersburg State University, University pr. 26, Old Peterhof, St. Petersburg, 198504 Russia. alextim@AT11692.spb.edu
Schaefer
Henry F
HF