Coordination complexes of thiazyl rings: Synthesis, structure and DFT computational analysis of CpCr(CO)x (x = 2,3) complexes of fluorinated and non-fluorinated 1lamda^3-1,2,4,6-thiatriazinyls, with differing Cr—S bond orders.

Simple item page
dc.contributor.authorAng, Chwee Y.
dc.contributor.authorKuan, Seah L.
dc.contributor.authorTan, Geok K.
dc.contributor.authorGoh, Lai Y.
dc.contributor.authorRoemmele, Tracey L.
dc.contributor.authorYu, Xin
dc.contributor.authorBoeré, René T.
dc.date.accessioned2019-03-31T23:44:05Z
dc.date.available2019-03-31T23:44:05Z
dc.date.issued2015
dc.descriptionSherpa Romeo green journal. Permission to archive accepted author manuscript.en_US
dc.description.abstractReaction of [3,5-Ph2-C2N3S]2 with [CpCr(CO)3]2 in toluene at RT forms an adduct via a Cr—S bond, formulated as CpCr(CO)3SN3C2Ph2, which has fitting NMR, IR and combustion analysis data. The structure was determined by a single-crystal X-ray structure diffraction study (P21/n, a = 8.4611(17)Å; b = 20.509(4) Å, c = 11.757(2) Å,  = 104.453(7)°). The Cr—S bond-length = 2.4908(11) Å corresponds to a bond-order of 1.0 from > 90 values for CpCr(CO)x or Cp*Cr(CO)x moieties (x = 2,3) bonded to S which are used to establish a Pauling-type bond order scale specific to this class of compounds. Similar reactions of fluorinated thiatriazinyls derived from [3-Ph-5-CF3-C2N3S]2 or [4-MeOC6H4-5-CF3-C2N3S]2 are accompanied by the loss of CO to produce CpCr(CO)2SN3C2PhCF3 (P, a = 8.0929(8) Å; b = 10.3160(10) Å, c = 11.2405(11),  = 70.032(2)°, = 72.076(2)°, = 82.375(2)° ) and CpCr(CO)2SN3(CCF3)(C6H4OCH3) (P21/c, a = 8.1311(7)Å; b = 24.284(2) Å, c = 9.1025(8) Å,  = 97.218(2)°), also fully characterized by spectroscopy and crystallography. Their measured Cr—S bond-lengths, 2.2987(14) Å and 2.2965(11) Å, correspond to bond orders of 1.5. (U/R)B3PW91/6-311+G(2df,2p)//B3PW91/6-31G(2d,p) hybrid DFT calculations show that the tricarbonyl complex has an unusual  bond. However, the dicarbonyl complexes of the fluorinated thiatriazinyls are -bonded.en_US
dc.description.peer-reviewYesen_US
dc.identifier.citationAng, C. Y., Kuan, S. L., Tan, G. K., Goh, L. Y., Roemmele, T. L., Yu, X., & Boeré, R. T. (2015). Coordination complexes of thiazyl rings: Synthesis, structure and DFT computational analysis of CpCr(CO)x (x = 2,3) complexes of fluorinatedand non-fluorinated 13-1,2,4,6-thiatriazinyls, with differing Cr—S bond orders. Canadian Journal of Chemistry, 2015, 93(2): 181-195, https://doi.org/10.1139/cjc-2014-0257en_US
dc.identifier.urihttps://hdl.handle.net/10133/5308
dc.language.isoen_USen_US
dc.publisherNRC Research Pressen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionNational University of Singaporeen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.urlhttps://doi.org/10.1139/cjc-2014-0257en_US
dc.subjectMultiple-bondsen_US
dc.subjectThiazyl radicalsen_US
dc.subjectTrifluoromethylen_US
dc.subjectChromium-sulfur bondsen_US
dc.subjectChromium-nitrogen bondsen_US
dc.subjectSingle crystal X-ray crystallographyen_US
dc.subjectDFT calculationsen_US
dc.titleCoordination complexes of thiazyl rings: Synthesis, structure and DFT computational analysis of CpCr(CO)x (x = 2,3) complexes of fluorinated and non-fluorinated 1lamda^3-1,2,4,6-thiatriazinyls, with differing Cr—S bond orders.en_US
dc.typeArticleen_US
Files
Original bundle
Now showing 1 - 2 of 2
Thumbnail Image
Name:
Boere-coordination-complexes-of-thiazyl.pdf
Size:
1.87 MB
Format:
Adobe Portable Document Format
Description:
Download
Thumbnail Image
Name:
Boeré-coordination-complexesVR.pdf
Size:
3.77 MB
Format:
Adobe Portable Document Format
Description:
REQUEST a copy of the final published version
Download
License bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
1.75 KB
Format:
Item-specific license agreed upon to submission
Description:
Download
Collections
Boere, Rene