Vinyliden-übergangsmetallkomplexe XXXVIII. Alkin-, alkinyl-, vinyliden-, allenyliden- und benzyl-rhodiumkomplexe mit dem phosphinoether iPr2PCH2CH2OMe als ein- und zweizähnigen Liganden
| Autor: | Bettina Windmüller, Justin Wolf, Helmut Werner |
|---|---|
| Rok vydání: | 1995 |
| Předmět: |
chemistry.chemical_classification
Stereochemistry Organic Chemistry Cationic polymerization Salt (chemistry) chemistry.chemical_element Alkyne Biochemistry Catalysis Rhodium Inorganic Chemistry chemistry.chemical_compound Monomer chemistry Octahedron Reagent Materials Chemistry Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 502:147-161 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/0022-328x(95)05784-m |
| Popis: | The monomeric four-coordinate rhodium(I) compound [RhCiL2] (L =iPr2PCH2CH2OMe) (1) reacts with terminal alkynes HCCR ( R = t Bu, Tol, CH(Ph)OH, C(Ph) 2 OH, C( i Pr ) 2 OH ) to give the vinylidene complexes trans-[RhCl(= C = CHRL)L2] (5–10) as the final products. Whereas for R = C(Ph)2OH, the stepwise conversion of the initially formed square-planar alkyne derivative 2 to the octahedral alkynyl(hydrido)compound 3 and further to the vinylidene complex 5 has been confirmed, for R = C( i Pr ) 2 OH a complete rearrangement of the isolated compound [RhH(C CR)Cl(κ2(P,O)-L)] (4) to the vinylidenerrhodium isomer 6 could not be achieved. The abstraction of water from 10 (R = C(Me)2OH) induced by catalytic amounts of CF3CO2H leads to the formation of the vinylvinylidenerhodium(I) compound trans-[RhCl(= C = CHC(Me) = CH2)L2] (11); on contrast, the corresponding reaction of 5 (R = C(Ph)2OH) with acidic Al2O3 yields the allenylidene complex trans-[RhCl(= C = C = CPh2L2] (12). The η[su3-benzylrhodium(I) compounds [Rh(η3-CH2C6H4-4-R)L2] (14,15), which are prepared from 1 and Grignard reagents 4-RC6H4CH2MgCl (R = H, CH3), react with CO to give the η1-benzyl derivatives [Rh(η1-CH2C6H4-4-R)(COLL2] (16, 17). The reaction of 14 with HCCC(iPr)2OH yields the bis(alkynyl)hydridorhodium(III) compound [RhH(CCR)2L2] ( R = C( i Pr) 2 OH ) (20), the structure of which has been determined by X-ray crystallography. While compound 14 reacts with HCCC(Me)2OH under an ethene atmosphere to give trans-[Rh(CC- -C(Me)2OH)(C2H4)L2] (21), on treatment of 14 with HCCTol in the presence of HBF4 the cationic complex [RhL2]BF4 (22a) is obtained. The corresponding PF6 salt 22b is prepared from [Rh(C8H14)2(OCMe2)2)2]PF6 and L. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect