TY  - JOUR
AB  - Metallodiphosphenes (eta5-C5R5) (CO)2M-P=P-Mes* (C5R5 = C5Me5, C5Me4Et, 1,2,4-iPr3CrH2, 1,3-tBu2C5H3,1,3-(Me3Si)2C5H3; M = Fe,Ru) undergo reaction with anhydrous hexafluoroacetone to afford either the five-membered metallaheterocycles (eta5-C5R5)(CO)M-P(=PMes*)OC-(CF3)2C(O) or metalated 1-oxa-2,3-diphosphetanes (eta5-C5R5)(CO)2M-P-P(Mes*)OC(CF3)2. It is demonstrated that the l-oxa-2,3-diphosphetanes result from an intramolecular rearrangement of the metallaheterocycles. The course of the reaction and the nature of the products is largely influenced by the basicity of the cyclopentadienylmetal fragment. The molecular structures of (eta5-C5Me5) (CO)Fe-P(=PMes*)OC(CF3)2C(O) (9a) (P2(1)/c, a = 21.809(4) angstrom, b = 10.066(2) angstrom, c = 16.250(3) angstrom, beta = 95.87(1)-degrees, (eta5-C5Me5)(CO)Ru-P=P(Mes*)OC(CF3)2C(O) (10a) (P2(1)/c, a = 22.308(8) angstrom, b = 10.174(4) angstrom, c = 16.014(10) angstrom, beta = 96.62(4)-degrees), (eta5-1,2,4-iPr3C6H2)(CO)Ru-P-(=PMes*)OC(CF3)2C(O) (10c) (P1BAR, a = 9.416(5) angstrom, b = 9.784(6) angstrom, c = 24.40(2) angstrom, alpha = 92.74(5)-degrees, beta = 98.42(5)-degrees, gamma = 117.37(4)-degrees), and (eta5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2 (11a) (C2/c, a = 46.79(3) angstrom, b = 9.316(5) angstrom, c = 16.611(5) angstrom, beta = 101.52(3)-degrees) were determined by single-crystal X-ray analyses.
DA  - 1994
DO  - 10.1021/om00018a012
LA  - eng
IS  - 6
M2  - 2194
PY  - 1994
SN  - 0276-7333
SP  - 2194-2204
T2  - Organometallics
TI  - Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2
UR  - https://nbn-resolving.org/urn:nbn:de:0070-pub-17746930
Y2  - 2024-11-22T07:20:09
ER  -