高等学校化学学报
高等學校化學學報
고등학교화학학보
Chemical Journal of Chinese Universities
2015年
11期
2241-2250
,共10页
彭彬%罗琼%李楠%张秀辉%李前树
彭彬%囉瓊%李楠%張秀輝%李前樹
팽빈%라경%리남%장수휘%리전수
密度泛函理论%BF配体%锇羰基化合物%理论研究
密度汎函理論%BF配體%鋨羰基化閤物%理論研究
밀도범함이론%BF배체%철탄기화합물%이론연구
Density functional theory(DFT)%BF ligand%Osimum carbonyl%Theoretical study
采用MPW1PW91和BP862种密度泛函方法对中性单核锇羰基化合物Os(BF)(CO)n(n=4,3)及双核锇羰基化合物Os2(BF)2(CO)n(n=7,6,5,4)进行理论计算研究,优化得到22个低能异构体。研究发现,单核配位饱和Os( BF)( CO)4的能量最低的异构体对称性为C2v ,其BF基团在三角双锥赤道面上。该异构体失去1个赤道面上的CO可得到Os(BF)(CO)3的能量最低异构体。单核Os(BF)(CO)n(n=4,3)的能量最低异构体的BF基团都位于配体三角双锥及缺顶点结构的赤道面上。配位饱和双核Os2(BF)2(CO)7有4个能量接近的异构体,其中能量最低的异构体结构中含有2个呈蝶形的桥配位BF基团。配位不饱和的Os2(BF)2(CO)6的2个能量接近的异构体结构相似,2个桥配位BF基团与2个Os原子构成平行四边形结构单元。配位不饱和的Os2(BF)2(CO)5和Os2(BF)2(CO)4的能量最低异构体都含有由2个桥配位BF基团与2个Os原子构成的平行四边形结构单元。双核Os2(BF)2(CO)n(n=7,6,5,4)能量最低异构体的BF基团都以桥配位形式和Os原子相连。离解能研究表明,单核配位饱和的Os(BF)(CO)4具有一定的热力学稳定性。双核的Os2(BF)2(CO)n(n=7,6)失去1个CO或者分裂为单核的Os(BF)(CO)4或Os(BF)(CO)3所需能量较高,表明其具有一定的热力学稳定性。
採用MPW1PW91和BP862種密度汎函方法對中性單覈鋨羰基化閤物Os(BF)(CO)n(n=4,3)及雙覈鋨羰基化閤物Os2(BF)2(CO)n(n=7,6,5,4)進行理論計算研究,優化得到22箇低能異構體。研究髮現,單覈配位飽和Os( BF)( CO)4的能量最低的異構體對稱性為C2v ,其BF基糰在三角雙錐赤道麵上。該異構體失去1箇赤道麵上的CO可得到Os(BF)(CO)3的能量最低異構體。單覈Os(BF)(CO)n(n=4,3)的能量最低異構體的BF基糰都位于配體三角雙錐及缺頂點結構的赤道麵上。配位飽和雙覈Os2(BF)2(CO)7有4箇能量接近的異構體,其中能量最低的異構體結構中含有2箇呈蝶形的橋配位BF基糰。配位不飽和的Os2(BF)2(CO)6的2箇能量接近的異構體結構相似,2箇橋配位BF基糰與2箇Os原子構成平行四邊形結構單元。配位不飽和的Os2(BF)2(CO)5和Os2(BF)2(CO)4的能量最低異構體都含有由2箇橋配位BF基糰與2箇Os原子構成的平行四邊形結構單元。雙覈Os2(BF)2(CO)n(n=7,6,5,4)能量最低異構體的BF基糰都以橋配位形式和Os原子相連。離解能研究錶明,單覈配位飽和的Os(BF)(CO)4具有一定的熱力學穩定性。雙覈的Os2(BF)2(CO)n(n=7,6)失去1箇CO或者分裂為單覈的Os(BF)(CO)4或Os(BF)(CO)3所需能量較高,錶明其具有一定的熱力學穩定性。
채용MPW1PW91화BP862충밀도범함방법대중성단핵철탄기화합물Os(BF)(CO)n(n=4,3)급쌍핵철탄기화합물Os2(BF)2(CO)n(n=7,6,5,4)진행이론계산연구,우화득도22개저능이구체。연구발현,단핵배위포화Os( BF)( CO)4적능량최저적이구체대칭성위C2v ,기BF기단재삼각쌍추적도면상。해이구체실거1개적도면상적CO가득도Os(BF)(CO)3적능량최저이구체。단핵Os(BF)(CO)n(n=4,3)적능량최저이구체적BF기단도위우배체삼각쌍추급결정점결구적적도면상。배위포화쌍핵Os2(BF)2(CO)7유4개능량접근적이구체,기중능량최저적이구체결구중함유2개정접형적교배위BF기단。배위불포화적Os2(BF)2(CO)6적2개능량접근적이구체결구상사,2개교배위BF기단여2개Os원자구성평행사변형결구단원。배위불포화적Os2(BF)2(CO)5화Os2(BF)2(CO)4적능량최저이구체도함유유2개교배위BF기단여2개Os원자구성적평행사변형결구단원。쌍핵Os2(BF)2(CO)n(n=7,6,5,4)능량최저이구체적BF기단도이교배위형식화Os원자상련。리해능연구표명,단핵배위포화적Os(BF)(CO)4구유일정적열역학은정성。쌍핵적Os2(BF)2(CO)n(n=7,6)실거1개CO혹자분렬위단핵적Os(BF)(CO)4혹Os(BF)(CO)3소수능량교고,표명기구유일정적열역학은정성。
Mononuclear and binuclear osmium fluoroborylene carbonyls Os ( BF ) ( CO ) n ( n=4 , 3 ) and Os2(BF)2(CO)n(n=7, 6, 5, 4) were investigated using MPW1PW91 and BP86 density functional theories. Twenty two isomers were obtained. For Os( BF) ( CO) 4 , the lowest-energy structure 14-1 is a singlet C2v sym-metrical trigonal bipyramid. The lowest energy structures for Os( BF) ( CO) 3 are derived from the trigonal bi-pyramidal Os( BF) ( CO) 4 structures by removal of a CO group. Four low energy isomers are predicted to be close in energy for Os2(BF)2(CO)7, the lowest-energy isomer, 27-1, has butterfly structure containing two bridging BF groups. For Os2(BF)2(CO)6. Two isomers, 26-1 and 26-2, are predicted to be nearly degenera-ted in energy. Both 26-1 and 26-2 are predicted to have two bridging BF groups. The global minimum isomer of Os2( BF) 2( CO) 5 and Os2( BF) 2( CO) 4 are similar to 26-1 with two BF groups bridging to two Os atoms. It seems that Os2(BF)2(CO)n(n=7, 6, 5, 4) are favored to form structures containing bridging fluoroborylene groups. The study of dissociation energy shows that the CO dissociation energy and dissociation energy of Os2(BF)2(CO)n(n=7, 6) into the mononuclear fragments Os(BF)(CO)4 or Os(BF)(CO)3 are large, suggesting those isomers are quite thermodynamically favorable.