Dunn, Simon C. published the artcileSynthesis and Reactions of Group 4 Imido Complexes Supported by Cyclooctatetraene Ligands, Recommanded Product: 2,4,6-Triisopropylbenzenethiol, the publication is Organometallics (2006), 25(7), 1755-1770, database is CAplus.
The reactions of the pseudo-two-coordinate Ti imido complexes [Ti(NtBu)(COT)] (1) (COT = ¦Ç8-C8H8), [Ti(NtBu)(COT”)] (2) (COT” = ¦Ç8-1,4-C8H6(SiMe3)2), and [Ti(NAr)(COT)] (3) (Ar = 2,6-iPr2C6H3) with a variety of organic substrates are reported. Reaction of 1 with CO2, tBuNCO, or ArNCO and reaction of 3 with CO2 or tBuNCO afforded the organic products tBuNCO, tBuNCNtBu, tBuNCNAr, ArNCO, and ArNCNtBu, resp., and a Ti oxo species. These reactions proceeded via an initial [2 + 2] cycloaddition to form an N,O-bound intermediate [Ti{N(R)C(O)R’}(COT)], which subsequently underwent a retrocycloaddn. to give an organic product and the Ti oxo species. In contrast, reaction of 3 with ArNCO gave the N,N-bound [2 + 2] cycloaddition product [Ti{N(Ar)C(O)N(Ar)}(COT)] (7). In general, the reactions of 1 and 3 with CS2 and isothiocyanates also resulted in an initial [2 + 2] cycloaddition to form an N,S-bound intermediate [Ti{N(R)C(S)R’}(COT)], which also subsequently underwent a retrocycloaddn. to give an organic product and a metal sulfide species. However, the N,S-bound compound [Ti{N(Ar)C(S)S}(COT)] (10) was stable to retrocycloaddn. and was isolated. Proton transfer reactions occurred between pinacol and compounds 1–3 to form the bis(alkoxide) species [Ti{OC(Me)2C(Me)2O}(COT)] (11) (from 1 or 3) or [Ti{OC(Me)2C(Me)2O}(COT”)] (12) (from 2) and the corresponding free amine. The reactions between 1–3 and 2 equiv of the thiols tBuSH and HS-2,4,6-iPr3C6H2 all resulted in the oxidation of the thiol to the disulfides tBuS-StBu and (2,4,6-iPr3C6H2)S-S(2,4,6-iPr3C6H2). Treatment of 1 with tBuNC in the presence of 1,3,5,7-cyclooctatetraene led to formal nitrene group transfer and the formation of the Ti(II) species [Ti(COT)(¦Ç4-C8H8)] (13) and tBuNCNtBu. The analogous reactions between 2 and 3 and tBuNC gave [Ti(NtBu)(COT”)(CNtBu)] (15) and [Ti(NAr)(COT)(CNtBu)] (17), and similarly the reaction between 1 and pyridine gave [Ti(NtBu)(COT)(py)] (19) (py = pyridine). Complex 19 was crystallog. characterized. DFT studies indicated that the interaction between pyridine and the Ti center in 19 and tBuNC and the Ti center in 17 was electrostatic in nature. [Ti(NR)(COT)(AlMe3-xClx)] (R = tBu, x = 0 (20); R = Ar, x = 0 (21); R = tBu, x = 1 (22); R = Ar, x = 1 (23)) were formed through the reactions of 1 and 3 with AlMe3 and AlMe2Cl, and DFT studies indicated that they contained four-membered metallacyclic rings. Attempts to prepare monomeric Zr imido cyclooctatetraene complexes through the reactions of [Zr2(¦Ì-NR)2Cl4(THF)x] (R = tBu, x = 3; R = 2,6-Me2C6H3(Ar’), x = 4) with K2COT, Li2COT”¡¤1.8(THF), or Li2[COT*] (COT* = 1,4-C8H6(SiMe2tBu)2) were unsuccessful. Only the crystallog. characterized dimeric species [Zr2(¦Ì-NAr’)2(COT”)2] (24) was isolated.
Organometallics published new progress about 22693-41-0. 22693-41-0 belongs to catalysis-chemistry, auxiliary class Other Functionalization Reagent, name is 2,4,6-Triisopropylbenzenethiol, and the molecular formula is C15H24S, Recommanded Product: 2,4,6-Triisopropylbenzenethiol.
Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia