264196-35-2Relevant articles and documents
Synthesis of Dinuclear Rhodium Complexes with 1,3-Butadiyndiyl Bridges. Coupling of the C4 and the Two C2 Units of a C2RhC4RhC2 Chain
Gil-Rubio, Juan,Laubender, Matthias,Werner, Helmut
, p. 1365 - 1372 (2000)
Compounds trans-[RhF(=C=CHR)(PiPr3)2] (2-4), of which 2 (R = H) was prepared for the first time from [Rh{η2-O2S(O)CF3}(PiPr3) 2], C2H2, and KF, reacted with Ph3SnC≡C-C≡CSnPh3 to give the dinuclear C4-bridged rhodium(I) complexes trans,trans-[{Rh(=C=CHR)-(PiPr3)2} 2(μ-C≡C-C≡C)] (5-7) in 78-88% isolated yield. On a similar route, by using trans-[RhF(CX)(PiPr3)2] (8, CX = CNC6H3Me2-2,6; 9, CX = CO) and Ph3SnC≡C-C≡CSnPh3 in the molar ratio of 2:1 as the starting materials, the diisocyanidedirhodium and dicarbonyldirhodium derivatives trans,trans-[{Rh(CX)(PiPr3)2} 2(μ-C≡C-C≡C)] (12,13) were obtained. The reactions of 8 and 9 with equimolar amounts of Ph3SnC≡C-C≡CSnPh3 gave the mononuclear complexes trans-[Rh(C≡C-C≡CSnPh3)(CX)(PiPr3) 2] (10,11), which on further treatment with 8 or 9 afforded the dinuclear compounds 12 and 13, respectively. The C-SnPh3 bond of 10 could be cleaved both by Al2O3/H2O and trans-[RhF(=C=CHPh)(PiPr3)2] (3) to give the butadiynyl compound trans-[Rh(C≡C-C≡CH)(CNC6H3Me 2-2,6)(PiPr3)2] (14) and the unsymmetrical dirhodium complex trans,trans-[{Rh(=C=CHPh)(PiPr3)2}{Rh-(CNC 6H3Me2-2,6)(PiPr3) 2}(μ-C≡C-C≡C)] (15). Moreover, treatment of 5 and 6 with CNC6H3-Me2-2,6 or CO led to a 2-fold migratory insertion reaction to yield the novel dinuclear compounds trans,trans-[{Rh(CX)(PiPr3)2} 2{μ-C(=CHR)C≡C-C≡C-C(CHR)}] (16-18), which contain a highly unsaturated eight-membered C8 chain as a bridge. The molecular structure of 17 (CX = CO; R = Ph) was determined by X-ray crystallography.
