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)†

doi:10.7503/cjcu20150636

Abstract

Abstract:

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 C₂_v 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.

Key words: Density functional theory(DFT), BF ligand, Osimum carbonyl, Theoretical study

CLC Number:

O641

TrendMD:

PENG Bin, LUO Qiong, LI Nan, ZHANG Xiuhui, LI Qianshu. 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)^†[J]. Chem. J. Chinese Universities, 2015, 36(11): 2241.

Figures/Tables 7

References 33

[1]	Calderazzo F., Leplattenier F., Inorg. Chem., 1967, 6, 1220—1224
[2]	Rushman P., van Buuren G. N., Shiralian M., Organometallics, 1983, 2(5), 693—694
[3]	Corey E. R., Dahl L. F., J. Am. Chem. Soc., 1961, 83, 2203—2204
[4]	Churchill M. R., Deboer B. G., Inorg. Chem., 1977, 16, 878—884
[5]	Moss J.R., Graham W. A. G.,Dalton Trans., 1977, 95—99
[6]	Bogdan P. L., Weitz E., J. Am. Chem. Soc., 1990, 112, 639—644
[7]	Xu B., Li Q. S., Xie Y., King R. B., Schaefer H. F., Inorg. Chem., 2008, 47, 3869—3878
[8]	Vidovic D., Aldridge S., Angew. Chem., 2009, 121, 3723—3726
[9]	Ehlers A. W., Baerends E. J., Bickelhaupt F. M., Radius U., Chem. A Euro. J., 1998, 4, 210—221
[10]	Radius U., Bickelhaupt F. M., Ehlers W. A., Goldberg N., Hoffmann R., Inorg. Chem., 1998, 37, 1080—1090
[11]	Bickelhaupt F. M., Radius U., Ehlers W. A., Hoffmann R., Baerends E. J., New J. Chem., 1998, 22, 1—3
[12]	Chen Y., Frenking G., J. Chem. Soc., Dalton Trans., 2001, 434—440
[13]	Frenking G., Fröhlich N., Chem. Rev., 2000, 100, 717—774
[14]	Xu L. C., Li Q. S., Xie Y. M., King R. B., Schaefer H. F., Inorg. Chem., 2010, 49, 1046—1055
[15]	Xu L. C., Li Q. S., Xie Y. M., King R. B., Schaefer H. F., Inorg. Chem., 2010, 49, 2996—3001
[16]	Xu L. C., Li Q. S., Xie Y. M., King R. B., Schaefer H. F., Organometallics, 2011, 30, 5084—5087
[17]	Bertsch S., Braunschweig H., Christ B., Forster M., Schwab K., Radacki K., Angew. Chem. Int. Ed., 2010, 49, 9517—9520
[18]	Braunschweig H., Damme A., Dewhurst R. D., Vargas A., Nature Chem., 2013, 5, 115—121
[19]	Braunschweig H., Shang R., Inorg. Chem., 2015, 54, 3099—3106
[20]	Hou N., Li Y., Wu D., Li Z. R., Chem. J. Chinese Universities, 2014, 35(4), 798—803
	(侯娜, 李莹, 吴迪, 李志儒. 高等学校化学学报, 2014, 35(4), 798—803)
[21]	Becke A. D., Phys. Rev. A, 1988, 38, 3098—3100
[22]	Perdew J. P., Phys. Rev. B, 1986, 33, 8822—8824
[23]	Adamo C., Barone V., J. Chem. Phys., 1998, 108, 664—675
[24]	Dolg M., Stoll H., Preuss H., Theoretica Chimica Acta, 1993, 85, 441—450
[25]	Andrae D., Haussermann U., Dolg M., Theoretica Chimica Acta, 1990, 77, 123—141
[26]	Dunning T. H., J. Chem. Phys., 1970, 53, 2823—2833
[27]	Huzinaga S., J. Chem. Phys., 1965, 42, 1293—1302
[28]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Keith T., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision D01: Gaussian Inc., Wallingford CT, 2013
[29]	Feng X., Gu J., Xie Y. M., King R. B., Schaefer H. F., J. Chem. Theor. Compt., 2007, 3, 1580—1587
[30]	Peng B., Li Q. S., Xie Y. M., King R. B., Schaefer H. F., Dalton Trans., 2008, 48, 6977—6986
[31]	Xie Y. M., Schaefer H. F., King R. B., J. Am. Chem. Soc., 2000, 122, 8746—8761
[32]	Li Q.S., Xu B., Xie Y. M., King R. B., Schaefer H. F.,Dalton Trans., 2007, 4312—4322
[33]	Xu B., Li Q. S., Xie Y. M., King R. B., Schaefer H. F., Croatica Chemica Acta, 2009, 82, 207—218

Related Articles 15

[1]	HE Hongrui, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220196.
[2]	WANG Yuanyue, AN Suosuo, ZHENG Xuming, ZHAO Yanying. Spectroscopic and Theoretical Studies on 5-Mercapto-1，3，4-thiadiazole-2-thione Microsolvation Clusters [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220354.
[3]	YING Fuming, JI Chenru, SU Peifeng, WU Wei. λ-DFCAS： A Hybrid Density Functional Complete Active Space Self Consistent Field Method [J]. Chem. J. Chinese Universities, 2021, 42(7): 2218.
[4]	CAO Hongyu,MA Zihui,ZHANG Wenqiong,TANG Qian,LI Ruyu,ZHENG Xuefang. Structures and Electronic Absorption Spectra of N/Neo-Confused, Doubly N-Confused and Neo-Confused N-Confused Porphyrin Isomers ^† [J]. Chem. J. Chinese Universities, 2020, 41(2): 341.
[5]	WEI Xin, DENG Yaoliang, ZHENG Xuming, ZHAO Yanying. Ground Structure and Excited State Proton Transfer Reaction of 2-Aminobenzothiazole [J]. Chem. J. Chinese Universities, 2019, 40(8): 1679.
[6]	ZHI Shasha,BAN Ying,XU Zhiguang,XU Xuan. Electron Transport of Metal String Complexes of [MM'M″(dpa)₄(Cl)₂](M=Co, Ni; M',M″=Co, Rh)^† [J]. Chem. J. Chinese Universities, 2019, 40(5): 980.
[7]	LIU Qiuna,XU Wenwen,LIU Maozhu,WANG Huigang,ZHENG Xuming. Study on Raman Spectroscopy Non-coincidence Effect of Propionic Anhydride C=O Vibration Mode^† [J]. Chem. J. Chinese Universities, 2019, 40(5): 932.
[8]	ZHOU Xiaofeng,ZHOU Yanbing,TANG Chunmei. Hydrogen Storage Capacity of the Alkaline Earth Metal Mg Exohedral Doped Boron Cage B₄₀M $g 6 †$ [J]. Chem. J. Chinese Universities, 2019, 40(3): 473.
[9]	ZHOU Hegen,JIN Hua,GUO Huirui,LIN Jing,ZHANG Yongfan. Electronic Structures and Optical Properties of Cu-based Semiconductors with Chalcopyrite-type Structure^† [J]. Chem. J. Chinese Universities, 2019, 40(3): 518.
[10]	YANG Yejin,YOU Jinglin,WANG Jian,WANG Min,HE Yingxia,WU Zhidong. In-situ High Temperature Raman Spectroscopic and Decomposition Thermodynamic Study of the Structure of Potassium Hydrogen Sulfate and Its Melt^† [J]. Chem. J. Chinese Universities, 2018, 39(10): 2272.
[11]	WANG Junkai, HAN Lei, HUANG Liang, ZHANG Haijun, LI Junyi, LI Saisai. Density Functional Theory Calculation and Experimental Study of Catalytic Synthesis SiC Nano Powders^† [J]. Chem. J. Chinese Universities, 2017, 38(9): 1602.
[12]	ZHANG Hui, ZHANG Hongmei, WANG Lianjun, SHEN Jinyou. Density Functional Theory Studies on the CO₂ Absorption by 1-Ethylamine-3-methylimidazolium Tetrafluoroborate^† [J]. Chem. J. Chinese Universities, 2016, 37(9): 1660.
[13]	MA Changmin, LIU Tingyu, CHANG Qiuxiang, LUO Guoyin. Theoretical Studies on the Intrinsic Defects in ZnO and ZnS Crystal^† [J]. Chem. J. Chinese Universities, 2016, 37(5): 932.
[14]	YANG Bingxing, YE Liping, GU Huijie, XU Huasheng, LUO Yong, LI Huiying. Theoretical Studies on the Structure and Adsorption Properties of Isomorphously Substituted FAU Zeolite^† [J]. Chem. J. Chinese Universities, 2016, 37(11): 2018.
[15]	TANG Yanhui, WANG Zhidong. Theoretical Studies on the Regioselectivity and Stereoselectivity of the Olefin Polymerization Catalyzed by Bridged-metallocene Complexes^† [J]. Chem. J. Chinese Universities, 2016, 37(10): 1849.

Isomer	MPW1PW91		BP86
Isomer	BF	CO	BF	CO
14-1	1517(763)	2097(1446), 2121(308), 2128(1619), 2205(69)	1460(691)	1977(1209), 1998(259), 2005(1357), 2078(50)
14-2	1558(677)	2091(1464), 2091(1464), 2126(334), 2191(359)	1501(611)	1974(1213), 1974(1213), 2001(303), 2062(281)
13-1	1515(793)	2082(1118), 2097(1885), 2178(67)	1465(703)	1961(911), 1970(1502), 2045(72)

Isomer	MPW1PW91		BP86
Isomer	BF	CO	BF	CO
14-1	1517(763)	2097(1446), 2121(308), 2128(1619), 2205(69)	1460(691)	1977(1209), 1998(259), 2005(1357), 2078(50)
14-2	1558(677)	2091(1464), 2091(1464), 2126(334), 2191(359)	1501(611)	1974(1213), 1974(1213), 2001(303), 2062(281)
13-1	1515(793)	2082(1118), 2097(1885), 2178(67)	1465(703)	1961(911), 1970(1502), 2045(72)

Isomer	MPW1PW91		BP86
Isomer	BF	CO	BF	CO
27-1	1387(669), 1405(255)	2097(250), 2113(628), 2118(1679), 2131(1222), 2140(520), 2154(1812), 2207(139)	1337(622), 1353(219)	1977(22), 1989(545), 1994(1642), 2007(1005), 2014(423), 2028(1599), 2076(131)
27-2	1381(758), 1401(118)	2077(962), 2096(428), 2139(972), 2147(1872), 2153(1618), 2154(134), 2227(141)	1329(672), 1349(117)	1960(723), 1978(360), 2014(811), 2022(1429), 2022(1774), 2027(35), 2093(143)
27-3	1348(452), 1540(801)	2098(67), 2102(486), 2117(551), 2133(2562), 2136(948), 2159(706), 2213(135)	1295(412), 1483(727)	1978(45), 1981(268), 1994(659), 2009(2137), 2010(787), 2036(609), 2084(106)
27-4	1384(666), 1408(399)	1969(620), 2123(0), 2124(0), 2129(1714), 2131(1884), 2159(2138), 2197(3)	1335(610), 1356(335)	1867(476), 1999(0), 2000(11), 2004(1593), 2005(1453), 2031(1920), 2066(0)
27-5	1533(1222), 1539(329)	1893(774), 2096(0), 2107(152), 2128(1250), 2128(2637), 2148(390), 2202(94)	1476(1133), 1481(293)	1803(613), 1975(0), 1984(156), 2002(1079), 2004(2194), 2024(379), 2073(67)
26-1	1361(740), 1389(0)	2111(0), 2116(2273), 2126(0), 2129(1699), 2158(2177), 2192(0)	1315(664), 1339(0)	1989(0), 1994(1955), 2001(0), 2004(1415), 2032(1742), 2061(0)
26-2	1351(546), 1398(206)	2108(0), 2119(2101), 2124(116), 2131(1677), 2159(2053), 2193(1)	1305(479), 1348(195),	1985(0), 1995(1778), 2000(104), 2006(1392), 2033(1660), 2061(0)
26-3	1346(336), 1403(580)	2101(16), 2115(0), 2122(1865), 2134(1373), 2159(2260), 2194(93)	1291(291), 1353(497)	1974(10), 1989(0), 1997(1580), 2006(1180), 2033(1803), 2061(54)
26-4	1368(458), 1532(859)	2087(1), 2094(809), 2116(706), 2121(2783), 2147(778), 2201(112)	1316(411), 1475(785)	1964(74), 1975(575), 1994(649), 1996(2205), 2024(725), 2070(80)
26-5	1306(252), 1541(1013)	1940(490), 2112(140), 2123(1918), 2130(832), 2153(1682), 2191(359)	1256(219), 1482(899)	1847(385), 1986(65), 1997(1690), 2005(646), 2025(1419), 2059(288)
25-1	1393(858), 1404(9)	2091(671), 2113(1625), 2124(894), 2137(2004), 2182(271)	1339(650), 1351(132)	1963(651), 1989(1273), 2000(714), 2006(1542), 2052(318)
25-2	1422(576), 1424(439)	1987(877), 2107(879), 2109(987), 2133(3156), 2171(8)	1370(495), 1374(413)	1865(637), 1983(682), 1986(850), 2008(2603), 2041(4)
25-3	1345(240), 1550(910)	1953(489), 2086(879), 2118(1361), 2135(1942), 2169(232)	1295(217), 1491(814)	1825(368), 1964(718), 1994(1163), 2008(1489), 2039(224)
25-4	1391(430), 1412(603)	2101(571), 2105(927), 2115(1317), 2141(2354), 2176(95)	1336(372), 1360(530)	1977(424), 1979(766), 1990(1158), 2017(1865), 2046(83)
25-5	1365(537), 1538(739)	2064(312), 2088(1047), 2108(2807), 2145(540), 2189(67)	1320(475), 1484(668)	1940(355), 1969(825), 1979(2167), 2017(572), 2055(67)
24-1	1391(951), 1394(13)	2079(0), 2092(2460), 2123(2125), 2156(158)	1339(594), 1345(266)	1952(0), 1964(1997), 1990(1763), 2020(98)
24-2	1391(347), 1548(799)	1887(844), 2085(1035), 2104(2053), 2143(619)	1344(323), 1491(721)	1776(611), 1958(850), 1977(1693), 2009(463)
24-3	1408(489), 1422(493)	2095(0), 2096(2037), 2125(2869), 2158(42)	1358(412), 1373(439)	1971(0), 1972(1673), 2000(2309), 2029(22)
24-4	1408(465), 1558(856)	2074(788), 2101(1677), 2121(1716), 2157(410)	1354(405), 1501(760)	1948(659), 1976(1361), 1992(1310), 2025(349)

Isomer	MPW1PW91		BP86
Isomer	BF	CO	BF	CO
27-1	1387(669), 1405(255)	2097(250), 2113(628), 2118(1679), 2131(1222), 2140(520), 2154(1812), 2207(139)	1337(622), 1353(219)	1977(22), 1989(545), 1994(1642), 2007(1005), 2014(423), 2028(1599), 2076(131)
27-2	1381(758), 1401(118)	2077(962), 2096(428), 2139(972), 2147(1872), 2153(1618), 2154(134), 2227(141)	1329(672), 1349(117)	1960(723), 1978(360), 2014(811), 2022(1429), 2022(1774), 2027(35), 2093(143)
27-3	1348(452), 1540(801)	2098(67), 2102(486), 2117(551), 2133(2562), 2136(948), 2159(706), 2213(135)	1295(412), 1483(727)	1978(45), 1981(268), 1994(659), 2009(2137), 2010(787), 2036(609), 2084(106)
27-4	1384(666), 1408(399)	1969(620), 2123(0), 2124(0), 2129(1714), 2131(1884), 2159(2138), 2197(3)	1335(610), 1356(335)	1867(476), 1999(0), 2000(11), 2004(1593), 2005(1453), 2031(1920), 2066(0)
27-5	1533(1222), 1539(329)	1893(774), 2096(0), 2107(152), 2128(1250), 2128(2637), 2148(390), 2202(94)	1476(1133), 1481(293)	1803(613), 1975(0), 1984(156), 2002(1079), 2004(2194), 2024(379), 2073(67)
26-1	1361(740), 1389(0)	2111(0), 2116(2273), 2126(0), 2129(1699), 2158(2177), 2192(0)	1315(664), 1339(0)	1989(0), 1994(1955), 2001(0), 2004(1415), 2032(1742), 2061(0)
26-2	1351(546), 1398(206)	2108(0), 2119(2101), 2124(116), 2131(1677), 2159(2053), 2193(1)	1305(479), 1348(195),	1985(0), 1995(1778), 2000(104), 2006(1392), 2033(1660), 2061(0)
26-3	1346(336), 1403(580)	2101(16), 2115(0), 2122(1865), 2134(1373), 2159(2260), 2194(93)	1291(291), 1353(497)	1974(10), 1989(0), 1997(1580), 2006(1180), 2033(1803), 2061(54)
26-4	1368(458), 1532(859)	2087(1), 2094(809), 2116(706), 2121(2783), 2147(778), 2201(112)	1316(411), 1475(785)	1964(74), 1975(575), 1994(649), 1996(2205), 2024(725), 2070(80)
26-5	1306(252), 1541(1013)	1940(490), 2112(140), 2123(1918), 2130(832), 2153(1682), 2191(359)	1256(219), 1482(899)	1847(385), 1986(65), 1997(1690), 2005(646), 2025(1419), 2059(288)
25-1	1393(858), 1404(9)	2091(671), 2113(1625), 2124(894), 2137(2004), 2182(271)	1339(650), 1351(132)	1963(651), 1989(1273), 2000(714), 2006(1542), 2052(318)
25-2	1422(576), 1424(439)	1987(877), 2107(879), 2109(987), 2133(3156), 2171(8)	1370(495), 1374(413)	1865(637), 1983(682), 1986(850), 2008(2603), 2041(4)
25-3	1345(240), 1550(910)	1953(489), 2086(879), 2118(1361), 2135(1942), 2169(232)	1295(217), 1491(814)	1825(368), 1964(718), 1994(1163), 2008(1489), 2039(224)
25-4	1391(430), 1412(603)	2101(571), 2105(927), 2115(1317), 2141(2354), 2176(95)	1336(372), 1360(530)	1977(424), 1979(766), 1990(1158), 2017(1865), 2046(83)
25-5	1365(537), 1538(739)	2064(312), 2088(1047), 2108(2807), 2145(540), 2189(67)	1320(475), 1484(668)	1940(355), 1969(825), 1979(2167), 2017(572), 2055(67)
24-1	1391(951), 1394(13)	2079(0), 2092(2460), 2123(2125), 2156(158)	1339(594), 1345(266)	1952(0), 1964(1997), 1990(1763), 2020(98)
24-2	1391(347), 1548(799)	1887(844), 2085(1035), 2104(2053), 2143(619)	1344(323), 1491(721)	1776(611), 1958(850), 1977(1693), 2009(463)
24-3	1408(489), 1422(493)	2095(0), 2096(2037), 2125(2869), 2158(42)	1358(412), 1373(439)	1971(0), 1972(1673), 2000(2309), 2029(22)
24-4	1408(465), 1558(856)	2074(788), 2101(1677), 2121(1716), 2157(410)	1354(405), 1501(760)	1948(659), 1976(1361), 1992(1310), 2025(349)

Dissociation reaction	MPW1PW91	BP86
Os₂(BF)₂(CO)₇(27-1) →Os₂(BF)₂(CO)₆(26-1) + CO	99.4	94.3
Os₂(BF)₂(CO)₆(26-1) →Os₂(BF)₂(CO)₅(25-1) +CO	175.8	161.8
Os₂(BF)₂(CO)₅(25-1) →Os₂(BF)₂(CO)₄(24-1) +CO	198.5	189.0
Os(BF)(CO)₄(14-1) →Os(BF)(CO)₃(13-1)+CO	187.6	180.8
Os₂(BF)₂(CO)₇(27-1) →Os(BF)(CO)₄(14-1) + Os(BF)(CO)₃(13-1)	240.5	208.9
Os₂(BF)₂(CO)₆(26-1) →2Os(BF)(CO)₃(13-1)	328.7	295.3
2Os₂(BF)₂(CO)₆(26-1) →Os₂(BF)₂(CO)₇(27-1)+ Os₂(BF)₂(CO)₅(25-1)	76.4	67.5
2Os₂(BF)₂(CO)₅(25-1) →Os₂(BF)₂(CO)₆(26-1)+ Os₂(BF)₂(CO)₄(24-1)	22.7	27.3

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)^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 7

References 33

Related Articles 15

Recommended Articles

Metrics

Comments