The reactions of triethylamine and ethyldiisopropylamine with RU~(CO)p'r~om oted by Fe2(C0)4(P- (C6H5)3)z(p-SCH2CHa3t) 27 0 "C have been studied. In addition to the previously reported major product (p-H)(p3-qz-CH3C=NCH2CH3)R~3(l()C,t 0h)e 9th ree other triruthenium products formed, (p-H)(p3- q3-CH2CH=NCH2CH3)Ru3(CO(2))g, (p-H)(p3-q3-CH3CC(H)C=N(CHzCH3)z)Ru3(3()C, Oa)ngd (p- H)(p3-q3-(CH3CHz)zN=C(H)C(H)CCHZ)(R4~),3 h(avCeO b)egen characterized by spectroscopic methods and in the case of 3 and 4 by solid-state structural investigations. Compounds 1 and 2 are structural isomers, both of which have undergone alkyl cleavage, while 3 and 4 result from C-C coupling of a Cz fragment to a (C2H4)N(CH2CH3f)r2a gment. In the reaction of the bulkier ethyldiisopropylamine under the same conditions as above, only two triruthenium-amine products are formed, (p-H),(p3-q2-HCC=N(CH- (CH3)2)2R~3(C0(5))9 a nd (p-H)(p3-sz-CC=N(CH(CH3)z)zRu3(6()C, wO)higc h were characterized by solid- state structural investigations and spectroscopic methods. It was found that 5 converts cleanly to 6 on heating, while the isomeric 1 and 2 or 3 and 4 do not interconvert. Variable-temperature 'H and 13C NMR studies revealed that the organic ligand in 3 and 4 exists in solution as two and four isomers, respectively. Mechanistic schemes are proposed that rationalize the formation of 1 and 2 versus 3 and 4 and tentatively explsin why the bulkier amine does not undergo any C-N bond cleavage. Compound 3 crystallizes in the P1 space group with a = 10.967 (3) A, b = 14.052 (4) A, c = 8.148 (2) A, a = 102.95 (2)"; /3 = 110.74 (2)", and y = 97.32 (3)". Least-squares refinement based on 3358 observed reflections gave a final R value of 0.043 (R, = 0.054). Compound 4 crystallizes in the monoclinic space group P2,/c with a = 12.223 (3) A, b = 8.347 (1) A, c = 21.787 (5) A, and /3 = 92.93 (2)". Least-squares refinement of 4585 observed reflections gave a final agreement factor of R = 0.041 (R, = 0.045). Compound 5 crystallizes in the orthorhombic space group P212121 with a = 15.444 (2) A, b = 16.693 (2) A, and c = 9.027 (1) A. Least-squares refinement of 3706 observed reflections gave a final agreement factor of R = 0.037 (R, = 0.039). Compound 6 crystallizes in the orthorhombic space group Pnma with a = 19.466 (4) A, b = 14.610 (2) A, and c = 8.167 (1) A. Least-squares refinement of 3224 observed reflections gave a final agreement factor of R = 0.035 (R, = 0.042).
CARBON NITROGEN CLEAVAGE AND CARBON CARBON COUPLING PROCESSES IN THE REACTIONS OF RU3(CO)12 WITH TERTIARY-AMINES
GOBETTO, Roberto;MILONE, Luciano;
1990-01-01
Abstract
The reactions of triethylamine and ethyldiisopropylamine with RU~(CO)p'r~om oted by Fe2(C0)4(P- (C6H5)3)z(p-SCH2CHa3t) 27 0 "C have been studied. In addition to the previously reported major product (p-H)(p3-qz-CH3C=NCH2CH3)R~3(l()C,t 0h)e 9th ree other triruthenium products formed, (p-H)(p3- q3-CH2CH=NCH2CH3)Ru3(CO(2))g, (p-H)(p3-q3-CH3CC(H)C=N(CHzCH3)z)Ru3(3()C, Oa)ngd (p- H)(p3-q3-(CH3CHz)zN=C(H)C(H)CCHZ)(R4~),3 h(avCeO b)egen characterized by spectroscopic methods and in the case of 3 and 4 by solid-state structural investigations. Compounds 1 and 2 are structural isomers, both of which have undergone alkyl cleavage, while 3 and 4 result from C-C coupling of a Cz fragment to a (C2H4)N(CH2CH3f)r2a gment. In the reaction of the bulkier ethyldiisopropylamine under the same conditions as above, only two triruthenium-amine products are formed, (p-H),(p3-q2-HCC=N(CH- (CH3)2)2R~3(C0(5))9 a nd (p-H)(p3-sz-CC=N(CH(CH3)z)zRu3(6()C, wO)higc h were characterized by solid- state structural investigations and spectroscopic methods. It was found that 5 converts cleanly to 6 on heating, while the isomeric 1 and 2 or 3 and 4 do not interconvert. Variable-temperature 'H and 13C NMR studies revealed that the organic ligand in 3 and 4 exists in solution as two and four isomers, respectively. Mechanistic schemes are proposed that rationalize the formation of 1 and 2 versus 3 and 4 and tentatively explsin why the bulkier amine does not undergo any C-N bond cleavage. Compound 3 crystallizes in the P1 space group with a = 10.967 (3) A, b = 14.052 (4) A, c = 8.148 (2) A, a = 102.95 (2)"; /3 = 110.74 (2)", and y = 97.32 (3)". Least-squares refinement based on 3358 observed reflections gave a final R value of 0.043 (R, = 0.054). Compound 4 crystallizes in the monoclinic space group P2,/c with a = 12.223 (3) A, b = 8.347 (1) A, c = 21.787 (5) A, and /3 = 92.93 (2)". Least-squares refinement of 4585 observed reflections gave a final agreement factor of R = 0.041 (R, = 0.045). Compound 5 crystallizes in the orthorhombic space group P212121 with a = 15.444 (2) A, b = 16.693 (2) A, and c = 9.027 (1) A. Least-squares refinement of 3706 observed reflections gave a final agreement factor of R = 0.037 (R, = 0.039). Compound 6 crystallizes in the orthorhombic space group Pnma with a = 19.466 (4) A, b = 14.610 (2) A, and c = 8.167 (1) A. Least-squares refinement of 3224 observed reflections gave a final agreement factor of R = 0.035 (R, = 0.042).
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