REACTIONS OF RHODIUM DIHYDRIDE COMPLEXES [RhH2(R-DAB)-(PR'3)2]+ WITH THE ACETYLENES CH3OOCC=CCOOCH3 AND HC=CC6H5 - CRYSTAL-STRUCTURE OF [RHC(CO2CH3)=C(CO2CH3)C(CO2CH3)=C(CO2CH3)-(C6H11N=CHCH=NC6H11)(PCH3(C6H5)2)H2O]ClO4

Marta Iglesias, Carmen del Pino, Josep Ros, Severino García Blanco, Sagrario M. Carrera

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Abstract

Title full: Reactions of rhodium dihydride complexes [RhH2(R-DAB)-(PR′3)2]+ with the acetylenes CH3OOCCCCOOCH3 and HCCC6H5. Crystal structure of [RhC(CO2CH3)C(CO2CH3)C(CO 2CH3C(CO2CH3)-(C6 H11NCHCHNC6H11){PCH3 (C6H5)2} H2O]ClO4 The products of the reactions between a series of rhodium cis-dihydride. cations [RhH2(R-DAB)(PR′32]+ A and the alkynes CH3OOCCCCOOCH3 (DMAD) and HCCC6H5 at room temperature and 40°C (CH2Cl2 reflux) have been characterized by 1H NMR, IR spectroscopy and elemental analysis. Hydrogen evolution was observed in all the reactions and there was no evidence of insertion of the alkyne into the RhH bond. From DMAD compounds with a 1/1 ratio Rh/DMAD were obtained at room temperature but in refluxing CH2Cl2, H2 and one molecule of phosphine are eliminated and two mols of DMAD incorporated to give, by dimerization of the acetylene, a metallocyclopentadiene complex. The molecular structure of one of these complexex[RhC(CO2CH3)C(CO2CH3 )C(CO2CH3)C(CO2CH3) (c-Hex-DAB)PCH3(C6H5)2 · H2O]ClO4, is reported. This compound, an intermediate in the cyclotrimerization of alkynes, crystallizes in the monoclinic system, space group P21/c, unit cell dimensions: a 16.720(1), b 12.357(1), c 21.573(1) Å, β 106.53(1), Z = 4. The structure was resolved by Patterson and Fourier methods and refined to R and Rw values of 0.062 and 0.045 respectively. Cyclotrimerization was observed in all the reactions of HCCC6H6 with A and crystals of composition C24H18,HCCC6H5)3, obtained. An intermediate compound, with a 1/2 ratio of Rh/HcCC6H5, with composition [Rh{NH2-DAB,CH3CH3}(HCCC6H 5)2P(C6H5)3] +[ClO4] has also been isolated. © 1988.
Original languageEnglish
Pages (from-to)89-102
JournalJournal of Organometallic Chemistry
Volume338
Issue number1
DOIs
Publication statusPublished - 5 Jan 1988

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