ISSN:
0947-6539
Keywords:
dinitrogen
;
hydrido complexes
;
insertions
;
olefins
;
rhodium
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reduction of the hydrido chloride complex [Rh(H)Cl{CH3C(CH2CH2-P(tBu)2)2}] (4) with NaH under a nitrogen atmosphere results in formation of two products: the dinitrogen complex [Rh(N2)-{CH3C(CH2P(tBu)2)2}] (2) and the unusual low-valent hydrido-olefin complex, [RhH{CH2=C(CH2CH2P(tBu)2)2}] (3). In the presence of N2, complexes 2 and 3 are in equilibrium in solution; 2 is about 2.9kcalmol-1 more stable than 3 + N2. Both complexes co-crystallize in the solid state; they occupy the same crystallographic site in the crystal lattice (P2-(1)/c; Z = 4; a = 12.173(2), b = 14.121 (3), c = 15.367 (3); α = 90, β = 106.50(3), γ = 90°). The mechanism of the reversible interconversion of 2 and 3 has been studied in detail. Complex 3 undergoes rapid olefin insertion/β-hydrogen elimination processes. The insertion rates were measured at different temperatures by saturation transfer NMR experiments, providing evidence for a highly organized late transition state (δS≠≈ - 40 e.u.), which can be caused by a concerted “trans migration”. This theoretically unfavorable process is assisted by a distortion from the ideal square-planar configuration, including a decrease of the P-Rh-P angle and some bias of the double bond toward the hydride as indicated by the X-ray crystal structure of 3. Under a nitrogen atmosphere, the intermediate formed upon olefin insertion is slowly trapped by free dinitrogen to form complex 2. The dinitrogen dissociation from 2 was found to be the rate-determining step for the overall interconversion of 2 and 3 (δG≠298 = 24.1 kcalmol-1).
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030214
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