Reactions of Aluminum, Gallium, and Indium (M) Atoms with Phosphine: Generation and Characterization of the Species M·PH<sub>3</sub>, HMPH<sub>2</sub>, and H<sub>2</sub>MPH
作者:Hans-Jörg Himmel、Anthony J. Downs、Tim M. Greene
DOI:10.1021/ic000837v
日期:2001.1.1
Upon deposition of Al, Ga, or In atoms (M) together with phosphine in a solid argon matrix, metal atom complexes M.PH3 are formed. Photolysis of the matrices at lambda = 436 nm results in the tautomerization of the adduct species to the insertion products HMPH2 and H2MPH. In addition, PH is formed from the reactions with Ga and In, with HMPH2 being its most likely precursor. Further photolysis into
将Al,Ga或In原子(M)与磷化氢一起沉积在固态氩气基质中后,形成了金属原子配合物M.PH3。λ= 436 nm时基质的光解作用导致加成物种类与插入产物HMPH2和H2MPH互变异构化。此外,PH是由与Ga和In的反应形成的,而HMPH2是其最可能的前体。进一步光解为550 nm附近HMPH2的最大吸收量会导致HMPH2分解,其中加合物M.PH3会部分重新形成,并进一步形成PH。H2MPH在这些条件下是光稳定的,但在紫外线(200 <或=λ<或= 400 nm)的作用下会分解。所有分子均已通过红外光谱鉴定,氘的作用以及与密度泛函理论(DFT)计算所预期的振动性质或与已知的相关分子的比较,都证明了这种归属。详细说明了产生的分析结果,它阐明了新分子的结构和性质以及提供或处理新分子的反应机理。