TY - JOUR
T1 - Theoretical studies on mononuclear and binuclear osmium fluoroborylene carbonyls Os (BF)(CO)n(n=4,3) and Os2(BF)2(CO)n (n=7,6,5,4)
AU - Peng, Bin
AU - Luo, Qiong
AU - Li, Nan
AU - Zhang, Xiuhui
AU - Li, Qianshu
N1 - Publisher Copyright:
© 2015, Higher Education Press. All right reserved.
PY - 2015/11/1
Y1 - 2015/11/1
N2 - 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 symmetrical trigonal bipyramid. The lowest energy structures for Os (BF)(CO)3 are derived from the trigonal bipyramidal 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 degenerated 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.
AB - 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 symmetrical trigonal bipyramid. The lowest energy structures for Os (BF)(CO)3 are derived from the trigonal bipyramidal 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 degenerated 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.
KW - BF ligand
KW - Density functional theory (DFT)
KW - Osimum carbonyl
KW - Theoretical study
UR - http://www.scopus.com/inward/record.url?scp=84949464222&partnerID=8YFLogxK
U2 - 10.7503/cjcu20150636
DO - 10.7503/cjcu20150636
M3 - Article
AN - SCOPUS:84949464222
SN - 0251-0790
VL - 36
SP - 2241
EP - 2250
JO - Kao Teng Hsueh Hsiao Hua Heush Hsueh Pao/ Chemical Journal of Chinese Universities
JF - Kao Teng Hsueh Hsiao Hua Heush Hsueh Pao/ Chemical Journal of Chinese Universities
IS - 11
ER -