CAJ | 학술논문

运用B3LYP/6-311+G?(LANL2DZ)详细地研究了Ru原子与N2分子相互作用的单端位直线型L-RuN2和单侧双配位S-RuN2及插入化合物NRuN弯曲型和直线型的不同自旋多重度下多个电子态的平衡几何结构、电子结构、轨道布居和振动光谱等性质,同时对构型转化和插入反应过渡态及反应的势能曲线进行了计算。结果表明两种构型的复合物中一般低能态Ru对N2的活化都不大,直线型的3Δ和3∑-相对基态反应物是能稳定存在的,轨道作用机制是σ/π授予与反馈。化合物NRuN与实验对照,13 B1和11A1态可能是实验所观察的,两种构型中众多电子态相对于Ru(a5F)+2N(4S)是稳定的。势能曲线体现插入反应能垒很高,生成NRuN化合物在热力学和动力学上都是不利的。
운용B3LYP/6-311+G?(LANL2DZ)상세지연구료Ru원자여N2분자상호작용적단단위직선형L-RuN2화단측쌍배위S-RuN2급삽입화합물NRuN만곡형화직선형적불동자선다중도하다개전자태적평형궤하결구、전자결구、궤도포거화진동광보등성질,동시대구형전화화삽입반응과도태급반응적세능곡선진행료계산。결과표명량충구형적복합물중일반저능태Ru대N2적활화도불대,직선형적3Δ화3∑-상대기태반응물시능은정존재적,궤도작용궤제시σ/π수여여반궤。화합물NRuN여실험대조,13 B1화11A1태가능시실험소관찰적,량충구형중음다전자태상대우Ru(a5F)+2N(4S)시은정적。세능곡선체현삽입반응능루흔고,생성NRuN화합물재열역학화동역학상도시불리적。
The geometrical and electronic structures, bonding properties, and vibrational frequencies of complex RuN2 and compound NRuN in linear and bent structures with different multiplicity and electronic states were studied by B3 LYP method using 6-311+G?and LANL2 DZ basis sets. The transition states for transformation between linear and bent structures and insertion reaction were calculated, and the potential energy curves ob-tained. The results indicate that N2 molecule was activated slightly in most stable electronic states of the comple-xes, 3Δand 3∑- states are more stable than the ground states of the reactants. There were some electrons trans-ferred from Ru atom to N2 molecule viaσ/πdonation and backing. Compared to experiment reported, the struc-ture and vibrational characteristics of compound NRuN in 13 B1 and 11 A1 states are agreed well and proposed as the plausible candidates for the experimental result. Most of electronic states of compound NRuN formed from Ru (a5F) +2N(4S) are exothermic. Ru atom direct insertion into the triple bonds N2 is much more difficult because the energy barriers are higher and the products are thermodynamic instability.