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.
Ang, Chwee Y.
Kuan, Seah L.
Tan, Geok K.
Goh, Lai Y.
Roemmele, Tracey L.
Boeré, René T.
NRC Research Press
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.
Sherpa Romeo green journal. Permission to archive accepted author manuscript.
Multiple-bonds , Thiazyl radicals , Trifluoromethyl , Chromium-sulfur bonds , Chromium-nitrogen bonds , Single crystal X-ray crystallography , DFT calculations
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