{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:48:49Z","timestamp":1760402929156,"version":"build-2065373602"},"reference-count":34,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2021,4,12]],"date-time":"2021-04-12T00:00:00Z","timestamp":1618185600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-1661604"],"award-info":[{"award-number":["CHE-1661604"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The geometries, energetics, and preferred spin states of the second-row transition metal tris(butadiene) complexes (C4H6)3M (M = Zr\u2013Pd) and their isomers, including the experimentally known very stable molybdenum derivative (C4H6)3Mo, have been examined by density functional theory. Such low-energy structures are found to have low-spin singlet and doublet spin states in contrast to the corresponding derivatives of the first-row transition metals. The three butadiene ligands in the lowest-energy (C4H6)3M structures of the late second-row transition metals couple to form a C12H18 ligand that binds to the central metal atom as a hexahapto ligand for M = Pd but as an octahapto ligand for M = Rh and Ru. However, the lowest-energy (C4H6)3M structures of the early transition metals have three separate tetrahapto butadiene ligands for M = Zr, Nb, and Mo or two tetrahapto butadiene ligands and one dihapto butadiene ligand for M = Tc. The low energy of the experimentally known singlet (C4H6)3Mo structure contrasts with the very high energy of its experimentally unknown singlet chromium (C4H6)3Cr analog relative to quintet (C12H18)Cr isomers with an open-chain C12H18 ligand.<\/jats:p>","DOI":"10.3390\/molecules26082220","type":"journal-article","created":{"date-parts":[[2021,4,12]],"date-time":"2021-04-12T11:05:06Z","timestamp":1618225506000},"page":"2220","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Tris(Butadiene) Compounds versus Butadiene Oligomerization in Second-Row Transition Metal Chemistry: Effects of Increased Ligand Fields"],"prefix":"10.3390","volume":"26","author":[{"given":"Yi","family":"Zhao","sequence":"first","affiliation":[{"name":"School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China"},{"name":"Research Institute of Petroleum Processing (RIPP), SINOPEC, Beijing 100083, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Qun","family":"Chen","sequence":"additional","affiliation":[{"name":"School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mingyang","family":"He","sequence":"additional","affiliation":[{"name":"School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8744-7897","authenticated-orcid":false,"given":"Zhihui","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xuejun","family":"Feng","sequence":"additional","affiliation":[{"name":"School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China"},{"name":"Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8091-5478","authenticated-orcid":false,"given":"Yaoming","family":"Xie","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Robert Bruce","family":"King","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Henry F.","family":"Schaefer","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,4,12]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1002\/jlac.19304820111","article-title":"\u00dcber Carbonyle und Nitrosyle. IV","volume":"482","author":"Reihlen","year":"1930","journal-title":"Liebigs Ann. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Hallam, B.F., and Pauson, P.L. (1958). Metal derivatives of conjugated dienes. Part I. Butadiene-and cyclohexadiene-iron tricarbonyls. J. Chem. Soc., 642\u2013645.","DOI":"10.1039\/jr9580000642"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1039","DOI":"10.1038\/1681039b0","article-title":"A new type of organo-iron compound","volume":"168","author":"Kealy","year":"1951","journal-title":"Nature"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"632","DOI":"10.1039\/jr9520000632","article-title":"Dicyclopentadienyliron","volume":"3","author":"Miller","year":"1952","journal-title":"J. Chem. Soc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"758","DOI":"10.1107\/S0365110X63001973","article-title":"Studies of some carbon compounds of the transition metals. IV. The structure of butadiene iron tricarbonyl","volume":"16","author":"Mills","year":"1963","journal-title":"Acta Crystallogr."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"397","DOI":"10.1016\/S0022-328X(00)82929-0","article-title":"The three-dimensional structure of trans-trans-trans-1,5,9-cyclododecatrienenickel","volume":"44","author":"Brauer","year":"1972","journal-title":"J. Organomet. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"5542","DOI":"10.1021\/acs.jpca.9b03063","article-title":"Tris(butadiene) metal complexes of the first row transition metals versus coupling of butadiene to eight and twelve-carbon hydrocarbon chains","volume":"123","author":"Fan","year":"2019","journal-title":"J. Phys. Chem. A"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"C49","DOI":"10.1016\/S0022-328X(00)93770-7","article-title":"Bis(\u03b74-2,3-dimethyl-1,3-butadiene) nickel","volume":"184","author":"Jolly","year":"1980","journal-title":"J. Organomet. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Cloke, F.G.N., and McCamley, A. (1991). Butadiene sandwich compounds\u2014Synthesis of bis(\u03b7-1,4-di-tert-butylbuta-1,3,-diene) complexes of titanium and vanadium. Chem. Commun., 1470\u20131471.","DOI":"10.1039\/C39910001470"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Cloke, F.G.N., Hitchcock, P.B., and McCamley, A. (1993). Synthesis and reactivity of bis(\u03b7-1,4-di-tert-butylbuta-1,3,-diene)cobalt\u2014The X-ray crystal structure of the anionic butadiene sandwich complex [K(18-crown-6)(thf)2][Co(\u03b7-C4H4But2)2]. Chem. Commun., 248\u2013250.","DOI":"10.1039\/C39930000248"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"245","DOI":"10.1016\/0022-328X(95)05736-9","article-title":"Bis{1,4-bis(trimethylsilyl) buta-1,3-diene}cobalt: Synthesis and molecular structure","volume":"507","author":"Cloke","year":"1996","journal-title":"J. Organomet. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"626","DOI":"10.1021\/ja00809a073","article-title":"Reactions of tungsten and molybdenum atoms with 1,3-butadiene. Tris(butadiene)tungsten and molybdenum","volume":"96","author":"Skell","year":"1974","journal-title":"J. Am. Chem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"201","DOI":"10.1002\/ange.19810930217","article-title":"Reduktive synthese und reaktivit\u00e4t von Tris (butadien) molybd\u00e4n und wolfram","volume":"93","author":"Gausing","year":"1981","journal-title":"Angew. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"5021","DOI":"10.1021\/om020525v","article-title":"Trigonal prismatic structure of tris(butadiene)molybdenum and related complexes revisited: Diolefin or metallacyclopentene coordination?","volume":"21","author":"Kaupp","year":"2002","journal-title":"Organometallics"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5931","DOI":"10.1021\/ic400145f","article-title":"Molybdenum 17- and 18-electron bis and tris(butadiene) complexes: Electronic structures, spectroscopic properties, and oxidative ligand substitution reactions","volume":"52","author":"Stephan","year":"2013","journal-title":"Inorg. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"5808","DOI":"10.1021\/ic200699f","article-title":"Homoleptic hexa and penta gallylene coordinated complexes of molybdenum and rhodium","volume":"50","author":"Bollermann","year":"2011","journal-title":"Inorg. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2695","DOI":"10.1021\/cr0307188","article-title":"Theoretical methods of potential use for studies of inorganic reaction mechanisms","volume":"105","author":"Ziegler","year":"2005","journal-title":"Chem. Rev."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1282","DOI":"10.1021\/ct6001187","article-title":"Geometries of transition-metal complexes from density-functional theory","volume":"2","author":"Kabrede","year":"2006","journal-title":"J. Chem. Theory Comput."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"3804","DOI":"10.1002\/anie.200600110","article-title":"A quantum chemical study of the quintuple bond between two chromium centers in [PhCrCrPh]: Trans-Bent versus linear geometry","volume":"45","author":"Brynda","year":"2006","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"8056","DOI":"10.1021\/ja101044c","article-title":"Hydrogen generation from alcohols catalyzed by ruthenium-triphenylphosphine complexes: Multiple reaction pathways","volume":"132","author":"Sieffert","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"7977","DOI":"10.1021\/ja201665x","article-title":"The directive of the protein: How does cytochrome P450 select the mechanism of dopamine formation?","volume":"133","author":"Schyman","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"12994","DOI":"10.1021\/ja205515u","article-title":"Tetrarhena-heterocycle from the palladium-catalyzed dimerization of Re2(CO)8(\u03bc-SbPh2)(\u03bc-H) exhibits an unusual host-guest behavior","volume":"133","author":"Adams","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"15464","DOI":"10.1021\/ja203157u","article-title":"Does compound I vary significantly between isoforms of cytochrome P450?","volume":"133","author":"Lonsdale","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"194101","DOI":"10.1063\/1.2370993","article-title":"A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions","volume":"125","author":"Zhao","year":"2006","journal-title":"J. Chem. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density functional exchange-energy approximation with correct asymptotic behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"8822","DOI":"10.1103\/PhysRevB.33.8822","article-title":"Density-Functional approximation for the correlation energy of the inhomogeneous electron gas","volume":"33","author":"Perdew","year":"1986","journal-title":"Phys. Rev. B"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"48","DOI":"10.1007\/s00214-001-0300-3","article-title":"Reparameterization of hybrid functionals based on energy differences of states of different multiplicity","volume":"107","author":"Reiher","year":"2001","journal-title":"Theor. Chem. Acc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"441","DOI":"10.1007\/BF01112983","article-title":"A combination of quasi-relativistic pseudopotential and ligand-field calculations for lanthanoid compounds","volume":"85","author":"Dolg","year":"1993","journal-title":"Theor. Chim. Acta"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1431","DOI":"10.1080\/00268979300103121","article-title":"Ab-initio energy-adjusted pseudopotentials for elements of groups 13\u201317","volume":"80","author":"Bergner","year":"1993","journal-title":"Mol. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2823","DOI":"10.1063\/1.1674408","article-title":"Gaussian basis functions for use in molecular calculations. I. Contraction of (9s5p) atomic basis sets for the first-row atoms","volume":"53","author":"Dunning","year":"1970","journal-title":"J. Chem. Phys."},{"key":"ref_33","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Revision, D.01, Gaussian Inc."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"175","DOI":"10.1016\/j.theochem.2006.05.010","article-title":"Concerning the precision of standard density functional programs: Gaussian, Molpro, NWChem, Q-Chem, and Gamess","volume":"768","author":"Papas","year":"2006","journal-title":"J. Mol. Struct. THEOCHEM"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/8\/2220\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T14:12:24Z","timestamp":1760364744000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/8\/2220"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,4,12]]},"references-count":34,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2021,4]]}},"alternative-id":["molecules26082220"],"URL":"https:\/\/doi.org\/10.3390\/molecules26082220","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2021,4,12]]}}}