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Reactivity of a dititanium bis(pentalene) complex toward heteroallenes and main-group element–element bonds
journal contribution
posted on 2023-06-09, 04:33 authored by Alexander F R Kilpatrick, Jennifer C Green, Geoff ClokeThe reactivity of the Ti-Ti double bond in (µ,?5:?5-Pn†)2Ti2 (1; Pn† = 1,4-{SiiPr3}2C8H4) toward isocyanide and heteroallene substrates, and molecules featuring homonuclear bonds between main-group elements (E–E) has been explored. Reaction of 1 with methyl isocyanide or 1,3-N,N'-di-p-tolylcarbodiimide resulted in the formation of the 1:1 adducts (µ,?5:?5-Pn†)2Ti2(µ,?2-CNMe) (2) and (µ,?5:?5-Pn†)2Ti2(µ-C{N(4-C6H4CH3)}2) (3), respectively, which are thermally stable up to 100 °C in contrast to the analogous adducts formed with CO and CO2. Reaction of 1 with phenyl isocyanate afforded a paramagnetic complex, [(?8-Pn†)Ti]2(µ,?2:?2-O2CNPh) (4), in which the “double-sandwich” architecture of 1 has been broken and an unusual phenyl-carbonimidate ligand bridges two formally Ti(III) centers. Reaction of 1 with diphenyl dichalcogenides, Ph2E2 (E = S, Se, Te), led to the series of Ti–Ti single-bonded complexes (µ,?5:?5-Pn†)2[Ti(EPh)]2 (E = S (5), Se (6), Te (7)), which can be considered the result of a 2e– redox reaction or a 1,2-addition across the Ti-Ti bond. Treatment of 1 with azobenzene or phenyl azide afforded [(?8-Pn†)Ti]2(µ-NPh)2 (8), a bridging imido complex in which the pentalene ligands bind in an ?8 fashion to each formally Ti(IV) center, as the result of a 4e– redox reaction driven by the oxidative cleavage of the Ti-Ti double bond. The new complexes 2–8 were extensively characterized by various techniques including multinuclear NMR spectroscopy and single-crystal X-ray diffraction, and the experimental work was complemented by density functional theory (DFT) studies.
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Publication status
- Published
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- Accepted version
Journal
OrganometallicsISSN
0276-7333Publisher
American Chemical SocietyExternal DOI
Issue
2Volume
36Page range
352-362Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2017-01-04First Open Access (FOA) Date
2017-12-21First Compliant Deposit (FCD) Date
2017-01-04Usage metrics
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