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.
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Date
2015
Authors
Ang, Chwee Y.
Kuan, Seah L.
Tan, Geok K.
Goh, Lai Y.
Roemmele, Tracey L.
Yu, Xin
Boeré, René T.
Journal Title
Journal ISSN
Volume Title
Publisher
NRC Research Press
Abstract
Reaction 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.
Description
Sherpa Romeo green journal. Permission to archive accepted author manuscript.
Keywords
Multiple-bonds , Thiazyl radicals , Trifluoromethyl , Chromium-sulfur bonds , Chromium-nitrogen bonds , Single crystal X-ray crystallography , DFT calculations
Citation
Ang, 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 13-1,2,4,6-thiatriazinyls, with differing Cr—S bond orders. Canadian Journal of Chemistry, 2015, 93(2): 181-195, https://doi.org/10.1139/cjc-2014-0257