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• W2091512264 endingPage "1235" @default.
• W2091512264 startingPage "1225" @default.
• W2091512264 abstract "Abstract [MCl(L 2 )] 2 (M = Ir, L 2 = 1,5‐cyclooctadiene; M = Rh, L 2 = norbornadiene) reacts with [2‐(1,3‐dioxolane‐2‐yl)phenyl]diphenylphosphane ( 1 ) to afford [MCl(L 2 )(P~O)] (M = Ir, 2 ; M = Rh, 3 ), in which the ligand is P‐monodentate. Complex 3 reacts with AgClO 4 to give [Rh(Nbd)(PO)]ClO 4 ( 4 ), in which the ligand is P,O‐bidentate. Complex 2 is static at room temp., whereas 3 and 4 undergo intramolecular exchanges, which are fast at room temperature and slow at 223 K. The conformational changes in 4 are still fast at 223 K. Complexes 2 – 4 react with CO to afford trans ‐[MCl(CO)(P~O) 2 ] (M = Ir, 5 ; M = Rh, 6 ) or trans ‐[Rh(CO) 2 (P~O) 2 ]ClO 4 ( 7 ). Cyclooctadiene complexes react with PPh 2 ( o ‐C 6 H 4 CHO) to afford [MClH(PPh 2 ( o ‐C 6 H 4 CO))(PO] (M = Ir, 8 ; M = Rh, 9 ), in which 1 is chelating. Complex 8 contains a single diastereomer, is static in the 303–213 K range and reacts with CO to form [IrClH(PPh 2 ( o ‐C 6 H 4 CO))(P~O)(CO)] ( 10 ). Complex 9 contains two diastereomers 9a / 9b in a 95:5 ratio that undergo interconversion, which is slow at low temperature, and reacts with CO to undergo reductive elimination of aldehyde, cleavage of the Rh–O bond and scrambling of phosphanes. A mixture of trans ‐[RhCl(CO)(κ 1 ‐PPh 2 ( o ‐C 6 H 4 CHO))(P~O)] ( 11 ), 6 and trans ‐[RhCl(CO)(κ 1 ‐PPh 2 ( o ‐C 6 H 4 CHO)) 2 ] is formed. Bubbling of nitrogen transforms 11 back into 9 . Compound 2 reacts with hydrogen to give the fluxional [IrCl(H) 2 (P~O)(PO)] ( 12 ) with trans P atoms and cis H atoms, which attains coalescence at 203 K. Complex 12 reacts with mono‐ or bidentate ligands to afford static [IrCl(H) 2 (P~O) 2 L] (L = CO, 13 ; py, 14 ; n PrNH 2 , 15 ) or [Ir(H) 2 (P~O) 2 (en)]BPh 4 ( 16 , en = ethylenediamine). Abstraction of halide from 12 affords [Ir(H) 2 (PO) 2 ]BPh 4 ( 17 ), which is fluxional owing to interconversion between only two of the possible four diastereomers, for which Δ H ‡ = 54.7 ± 0.7 kJ mol –1 and Δ S ‡ = 4.7 ± 0.2 J K –1 mol –1 . The X‐ray structures of 8 , 15 and 16 are also reported." @default.
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• W2091512264 date "2012-12-19" @default.
• W2091512264 modified "2023-10-16" @default.
• W2091512264 title "Iridium and Rhodium Complexes with the Hemilabile Ligand [2‐(1,3‐Dioxolane‐2‐yl)phenyl]diphenylphosphane – Behaviour in Solution and Structural Characterization" @default.
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• W2091512264 doi "https://doi.org/10.1002/ejic.201201188" @default.
• W2091512264 hasPublicationYear "2012" @default.
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