A New Class of Constrained-Geometry Metallocenes: Synthesis and Crystal Structure of a Carboranyl-Thiol-Appended Half-Sandwich Titanocene and Its Conversion to Halotitanocene

Organometallics

Volumn 22, Issue 24, 2003, Pages 4839-4841

  Wang, Jianhui ^a,b   Zheng, Chong ^a   Maguire, John A ^b   Hosmane, Narayan S ^a  

^a NORTHERN ILLINOIS UNIVERSITY   (United States)

^b SOUTHERN METHODIST UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; CATALYSTS; CHEMICAL BONDS; CRYSTAL STRUCTURE; HALOGENATION; HYDROLYSIS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS (CHEMICAL); X RAY DIFFRACTION ANALYSIS;

BINUCLEAR CATALYTIC SYSTEMS; CATALYST PRECURSORS;

ORGANOMETALLICS;

EID: 0344443691     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0340802     Document Type: Article

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33. -1, KBr cell); 3134 (br, s), 3052 (s, m), 3021 (s, m), 2960 (s, s), 2919 (s, s), 2863 (s, m), 2847 (s, s), 2582 (br, s), 1618 (s, w), 1398 (s, s), 1255 (s, s), 1117 (s, s), 1071 (s, s), 1024 (s, w), 794 (s, w), 702 (s, s).
34. 6): 3401 (s, w), 2958 (s, s), 2920 (s, s), 2845 (s, m), 2566 (vs, br), 1635 (m, s), 1465 (s, s), 1399 (s, s), 1380 (s, s), 1260 (s, s), 1097 (s, s), 1020 (s, s), 801 (vs, s), 705 (m, s).
35. 6): 2958 (s, s), 2920 (s, s), 2611 (m, s), 2588 (m, s), 2571 (m, s), 2555 (m, s), 1400 (s, s), 1262 (s, s), 1099 (vs, br), 1019 (s, s), 798 (vs, s), 730 (m, s), 705 (m, s).
36. 3NHCl (0.62 g, 1.30 mmol) incrementally at -78 °C. The resulting solution was stirred at 0 °C over a period of several hours and then slowly warmed to room temperature and stirred further overnight at this temperature to give a red solution. The solvents from the reaction mixture were pumped off, leaving a red solid, which was washed with n-hexane. The solid was then recrystallized from a toluene and hexane mixture to give red microcrystals, identified as 4, in 41% yield.
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38. -3. Of the 6261 reflections collected (26 = 3.88-50°), 4232 reflections were respectively considered as observed (I > 2σ(I)) and were corrected for Lorentz, polarization, and absorption effects (Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction of Area Detector Data; University of Göttingen, Göttingen, Germany, 1996). The structure was solved by direct methods and refined by full-matrix least-squares techniques using SHELXTL (Sheldrick, G. M. SHELXTL, Version 5.1; Bruker Analytical X-ray Systems, Madison, WI, 1997). All non-H atoms were refined anisotropically. The final refinements converged at R1 = 0.0618, wR2 = 0.1305, and GOF = 1.378.