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Synthesis of Rh(acac)H(GeEt3) (PCy3) and Rh(acac)H(SnPh3)(PCy3) and their reactions with alkynes

AuthorsEsteruelas, Miguel A. ; Lahoz, Fernando J. ; Oñate, Enrique ; Oro, Luis A. ; Rodríguez, Laura
Issue Date1996
PublisherAmerican Chemical Society
CitationOrganometallics 15(17): 3670-3678 (1996)
AbstractThe monoolefin complex Rh(acac)(cyclooctene)(PCy3) (1) reacts with HGeEt3 to give Rh(acac)H(GeEt3)(PCy3) (2). On treatment of 2 with methyl propiolate and phenylacetylene the complexes Rh(acac){η2-CH(GeEt3)=CHR}(PCy3) (R = CO2Me (3), Ph (4)) are obtained. The X-ray crystal structure analysis of 3 reveals that the coordination geometry around the rhodium center is almost square-planar with the olefin disposed perpendicular to the coordination plane of the rhodium atom. Complex 1 also reacts with HSnPh3. The reaction leads to Rh(acsc)H(SnPh3)(PCy3) (5). In the presence of methyl propiolate, phenylacetylene, and (trimethylsilyl)acetylene complex 5 affords the alkenyl compounds Rh-(acac){(E)-CH=CHR}(SnPh3)(PCy3) (R = CO2Me (6), Ph (7), SiMe3 (8)). Similarly, the reactions of 5 with diethyl acetylenedicarboxylate and diphenylacetylene yield Rh(acac)-(CR=CHR)(SnPh3)(PCy3) (R = CO2Et (9), Ph (10)). The addition of 1 equiv of 1-ethynyl-1-cyclohexanol to a pentane suspension of 5 leads to the hydroxyalkenyl derivative Rh(acac)-{(E)-CH=CHC(OH)(CH2)4CH2}(SnPh 3)(PCy3) (11). The structure of 11 was determined by X-ray analysis. The coordination geometry around the metal center can be rationalized as a square pyramid with the stannyl ligand in the apical position. Although the hydroxyalkenyl ligand of 11 is stable and does not dehydrate to give the corresponding α,β-unsaturated alkenyl compound, complexes of this type can be prepared from enynes. Thus, the reaction of 5 with 2-methyl-1-buten-3-yne leads to the α,β-unsaturated alkenyl complex Rh(acac){(E)-CH=CHC(CH3)=CH2}(SnPh3)(PCy 3) (12), whereas in the presence of 1,1-diphenyl-2-propyn-1-ol complex 5 affords the allenyl derivative Rh(acac)(CH=C=CPh2(SnPh3)(PCy3) (13).
Identifiersdoi: 10.1021/om9602926
issn: 0276-7333
e-issn: 1520-6041
Appears in Collections:(ICMA) Artículos
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