In:
Dalton Transactions, Royal Society of Chemistry (RSC), Vol. 51, No. 26 ( 2022), p. 10266-10271
Abstract:
Iridium( iii ) bis(thiophosphinite) complexes of the type [( R PSCSP R )Ir(H)(Cl)(py)] ( R PSCSP R = κ 3 -(2,6-SPR 2 )C 6 H 3 ) (R = t Bu, iPr, Ph) can be prepared from the ligand precursors 1,3-(SPR 2 )C 6 H 4 by C–H activation at Ir using [Ir(COE) 2 Cl] 2 or [Ir(COD)Cl] 2 . Optimisation of the protocol for complexation showed that direct cyclometallation in the absence or presence of pyridine, as well as C–H activation in the presence of H 2 are viable options that, depending on the phosphine substituent furnish the five-coordinate Ir( iii ) hydride chloride complexes 2-R or the base stabilised species 3-R in good yields. In case of the Ph PSCSP Ph ligand, P–S activation results in the formation of a thiophosphine stabilised Ir( iii ) hydride complex [( Ph PSCSP Ph )Ir(H)(Cl)(PPh 2 SH)] (4). Reaction of 2-tBu with H 2 in the presence of base furnishes an Ir( iii ) dihydride complex (5) via a labile Ir( iii ) dihydride–dihydrogen complex (6). All complexes are inactive for transfer dehydrogenation of cyclooctane in the presence of NaO t Bu and tert -butylethylene, likely due to decomposition of the Ir complex in the presence of base at higher temperature.
Type of Medium:
Online Resource
ISSN:
1477-9226
,
1477-9234
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
detail.hit.zdb_id:
1472887-4
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