Matches in SemOpenAlex for { <https://semopenalex.org/work/W2003309073> ?p ?o ?g. }
- W2003309073 endingPage "1019" @default.
- W2003309073 startingPage "1002" @default.
- W2003309073 abstract "We report the first reactivity study of a transition-metal benzimidamido complex, namely Cp*Ti{PhC(NiPr)2}{NC(ArF5)NOtBu} (5, ArF5 = C6F5). Reaction with CO2 and tBuNCO gave the cycloaddition products Cp*Ti{PhC(NiPr)2}{OC(O)N(C{ArF5}NOtBu)} and Cp*Ti{PhC(NiPr)2}{OC(NtBu)N(C{ArF5}NOtBu)} (10), respectively, whereas with CS2 slow extrusion of ArF5CN from 5 occurred to ultimately form Cp*Ti{PhC(NiPr)2}{SC(S)N(OtBu)}. Reaction of 5 with ArC(O)H (Ar = Ph, 4-C6H4Me, 4-C6H4tBu, 4-C6H4OMe, 4-C6H4NMe2, 4-C6H4CF3) also gave the isolable metallacyclic complexes Cp*Ti{PhC(NiPr)2}{N(C{ArF5}NOtBu)C(Ar)(H)O} (13) via reversible [2 + 2] cycloaddition reactions. In contrast, reaction with HC(O)NMe2 formed Me2N{NC(ArF5)NOtBu}H (16) within 1 h at room temperature. Upon heating, 10 and 13 also underwent retrocyclization, forming the organic products tBuNCNC(ArF5)NOtBu and ArC{NC(ArF5)NOtBu}H (14), respectively. Selected examples of 14 and 16 were studied by DFT and UV–visible spectroscopy. Addition of isonitriles tBuNC and XylNC (Xyl = 2,6-C6H3Me2) to Cp*Ti{PhC(NiPr)2}{NC(Ar)NOtBu} (Ar = ArF5 (5), 2,6-C6H3F2 (ArF2)) afforded the σ adducts Cp*Ti{PhC(NiPr)2}{NC(Ar)NOtBu}(CNR) (Ar = ArF5, R = tBu, Xyl (19); Ar = ArF2, R = Xyl). Subsequently, 19 formed Cp*Ti{PhC(NiPr)2}{NC(NOtBu)C6F4N(Xyl)C}(F) (20) via C–F bond activation. Reaction of 5 with 2 equiv of B(ArF5)3 gave Cp*Ti{PhC(NiPr)2}{ON(B{ArF5}3)C(ArF5)N(H)(B{ArF5}3)} with elimination of 2-methylpropene." @default.
- W2003309073 created "2016-06-24" @default.
- W2003309073 creator A5013065975 @default.
- W2003309073 creator A5034924745 @default.
- W2003309073 creator A5040767620 @default.
- W2003309073 creator A5079306493 @default.
- W2003309073 date "2014-02-03" @default.
- W2003309073 modified "2023-10-16" @default.
- W2003309073 title "Reactions of a Cyclopentadienyl–Amidinate Titanium Benzimidamido Complex" @default.
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