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Understanding the Borane Analogy in AlnHn+4 (n= 5-19): Unprecedented Stability of a Non-Wade—Mingos Cluster Al8H12 Fused by Two Td-like Al4H6.

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Title: Understanding the Borane Analogy in AlnHn+4 (n= 5-19): Unprecedented Stability of a Non-Wade—Mingos Cluster Al8H12 Fused by Two Td-like Al4H6.
Authors: Li-juan Fu1, Lin Jin1, Chang-bin Shao1, Yi-hong Ding1 yhdd@jlu.edu.cn
Source: Inorganic Chemistry. 6/7/2010, Vol. 49 Issue 11, p5276-5284. 8p.
Subjects: Boranes, Microclusters, Molecular dynamics, Conduction electrons, Photoelectron spectroscopy, Born-Oppenheimer approximation, Anions
Abstract: Contrasting the boranes BnHn+4 with rich chemistry, the alanes Al2H6 remain largely unknown in laboratory, except tar the simplest Al2FH6. Though recent experimental and theoretical studies have proved AlnHn+4 to be the borane analogues, whether or not the borane analogy can exist tar the more complicated AlnHn+4 is stilt unclear. In this paper, we tind that at the B3PW911 ZVP level, AlnHn+4 each has a nidosingte cluster ground structure as BJ-t,,4 tarn c 12. Far ri ∼ 12, the tusion duster becomes energetically more competitive than the single duster also as BJ-I,∼4. Thus, conceming the ground structures, the atanes AlnHn+4 (n=5-19) could be considered as the borane analogues. Remarkably, A18K12 has a navel closo(4)-cioso(4) dustertused by two T∼like subunits ALH6, tying only 0.49 kcat/mol above the single duster. The Born-Oppenheimer molecular dynamic simulation shows that the c!oso(4)-closo(4) tusion duster intrinsically has high kinetic stability, which can be ascribed to the rigidity of the TcALHu subunit. Since TAl4I-t6 has been experimentally characterized in a gas phase very recentiy, we strongly recommend that the unprecedented non-Wade-Mingos alane A15t-t12 can be effectively tormed via the direct dimerization between two T∼Al4He, with the reaction energy (-39.65 kcavmol) very similar to that of the known diatane (2A1H3 - At2l∼te, -35.27 kcatlmol). [ABSTRACT FROM AUTHOR]
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Abstract:Contrasting the boranes BnHn+4 with rich chemistry, the alanes Al2H6 remain largely unknown in laboratory, except tar the simplest Al2FH6. Though recent experimental and theoretical studies have proved AlnHn+4 to be the borane analogues, whether or not the borane analogy can exist tar the more complicated AlnHn+4 is stilt unclear. In this paper, we tind that at the B3PW911 ZVP level, AlnHn+4 each has a nidosingte cluster ground structure as BJ-t,,4 tarn c 12. Far ri ∼ 12, the tusion duster becomes energetically more competitive than the single duster also as BJ-I,∼4. Thus, conceming the ground structures, the atanes AlnHn+4 (n=5-19) could be considered as the borane analogues. Remarkably, A18K12 has a navel closo(4)-cioso(4) dustertused by two T∼like subunits ALH6, tying only 0.49 kcat/mol above the single duster. The Born-Oppenheimer molecular dynamic simulation shows that the c!oso(4)-closo(4) tusion duster intrinsically has high kinetic stability, which can be ascribed to the rigidity of the TcALHu subunit. Since TAl4I-t6 has been experimentally characterized in a gas phase very recentiy, we strongly recommend that the unprecedented non-Wade-Mingos alane A15t-t12 can be effectively tormed via the direct dimerization between two T∼Al4He, with the reaction energy (-39.65 kcavmol) very similar to that of the known diatane (2A1H3 - At2l∼te, -35.27 kcatlmol). [ABSTRACT FROM AUTHOR]
ISSN:00201669
DOI:10.1021/ic100429b