Journal of Organometallic Chemistry p. 43 - 49 (1996)
Update date:2022-07-29
Topics:
Steinborn, Dirk
Yang, Lin
Aisa, A.M. Ahmed
[Rh]- ([Rh] = [Rh(dmgH)2(PPh3)]; dmgH2 = dimethylgluoxime), prepared by reduction of [Rh(dmgH)2(PPh3)Cl] with NaBH4 in methanolic KOH, reacts with cis/trans-XCH=CHCH2X (X = Cl, Br) to give the σ-allyl complexes cis/trans-[Rh]-CH2CH=CHX (X = Cl: 2a/b; X = Br: 3a/b) and cis/trans-[Rh]-CH2CH=CHOMe (4a/b). Propargyl halides react with [Rh]- to give [Rh]-CH2C≡CH (6) as well as [Rh]-CH=C=CH2 (7a) and [Rh]-C≡CMe (8). 7a isomerizes to give 8. In contrast, the dimethyl substituted propargyl chloride HC≡CCMe2Cl (9) reacts with [Rh]- to give [Rh]-CH=C=CMe2 (7b) exclusively. The addition of [Rh]- on HC≡CCH2OH (10a) and on HC≡CCH2OSiMe3 (10b) does not proceed regioselectively as the formation of [Rh]-CH=CHCH2OH (11a) and [Rh]-C(CH2OH)=CH2 (11b) show. [Rh]- reacts with HC≡CCH2SiMe3 (13) under addition on the C2 atom and C-Si bond cleavage to give [Rh]-CMe=CH2 (14). All compounds were characterized by 1H-, 13C-and 31P-NMR spectroscopy. With the coupling constant 1J(103Rh,31P) as a measure, the following trend in the tram influence of organo ligands was obtained: alkyl ≥ phenyl ～ vinyl > allyl > allenyl > alkinyl ～ propargyl.
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