ISSN:
0009-2940
Keywords:
Ruthenium(II) complexes, octahedral
;
Phosphino esters as mono- and bidentate ligands
;
Fluxional behaviour
;
Carbene complexes
;
Vinylidene complexes
;
Allenylidene complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Vinylidene Transition-Metal Complexes, XXXV[1]. - The Supporting Role of Phosphino Ester Ligands for the Synthesis of Neutral Carbene, Vinylidene and Allenylidene Ruthenium(II) ComplexesThe reaction of [RuCl2(PPh3)3] (1) with the phosphino esters iPr2P(CH2)nCO2R (2-4) leads to complete (n = 1; R = CH3, C2H5) or partial (n = 2; R =CH3) displacement of the PPh3 ligands and formation of the octahedral ruthenium(II) complexes [RuCl2{k2(P,O)-iPr2PCH2CO2R}2] (5, 6) and [RuCl2(PPh3){k(P)-iPr2PCH2CH2CO2Me}{k2(P,O)-iPr2PCH2CH2CO2Me}] (7). Treatment of 5 with LiBr and LiI affords the dibromo- and diiodoruthenium derivatives 8 and 9. While compound 5 reacts with CO and SO2 by cleavage of one Ru - O bond to yield the 1:1 adducts [RuCl2(L){k(P)-iPr2PCH2CO2Me}{k2(P,O)-iPr2PCH2CO2Me}] (10, 11), the reaction of the dibromo derivative 8 with CO in solution gives the dicarbonyl complex [RuBr2(CO)2{k(P)-iPr2PCH2CO2Me}2](13). If CO is passed over 8 in the solid state, the corresponding monocarbonyl compound 14 is formed. The hydridoruthenium(II) complex 16, which is obtained from equimolar amounts of [RuHCl(CO)(PiPr3)2] (15) and 2, reacts with HC≡CMe by insertion to give the vinyl derivative [RuCl{E - CH=CHMe}(CO)(PiPr3){k2(P,O)-iPr2CH2CO2Me}] (17). Treatment of 5 with HC̊' (R' = H, Me, tBu, Ph) and of 6, 8, 9 with HC≡CPh affords upon photochemical activation the octahedral vinylidene complexes [RuX2-(=C=CHR){k(P)-iPr2PCH2CO2R}{k2(P,O)-iPr2PCH2CO2R}] (18-21 and 23-25) in good to excellent yield. At room temperature, these compounds (with the exception of 25) are highly fluxional in solution. From 31P-NMR measurements, the free energies of activation ΔG
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951280108
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