395072-09-0Relevant academic research and scientific papers
Synthesis of rhodium complexes of an asymmetric η5,η1,η1-cyclo-pentadienyl- bis(phosphine) ligand by regioselective intramolecular dehydrofluorinative C-C coupling
Bellabarba, Ronan M.,Nieuwenhuyzen, Mark,Saunders, Graham C.
, p. 78 - 88 (2001)
The reaction between [{(η5-C5Me4H)RhX2} 2] and (C6F5)2PCH2CH2P(C 6F5)2 (dfppe) proceeds in refluxing benzene via cleavage of two C-F bonds and C-H bonds of adjacent methyl groups and formation of two C-C bonds to yield selectively the asymmetric cation [{η5,η1,η1-C5HMe 2-3,4-[CH2-2-C6F4P(C 6F5)CH2]2-1,2}RhX]+. The selectivity for X = Cl was determined to be >90%. Treatment of [(η5-C5Me4H)RhCl(dfppe)]BF4 with proton sponge afforded [{η5,η1,η1-C5HMe 2-3,4-[CH2-2-C6F4P(C 6F5)CH2]2-1,2}RhCl]BF4 exclusively. The regioselectivity displayed by these reactions is in stark contrast to that in the reaction between [(Cp*RhX2)2] and dfppe, and that between [Cp*RhCl(dfppe)]+ and proton sponge, in which C-H bonds of methyl groups in a 1,3 disposition are cleaved to yield the cation [{η5,η1,η1-C5Me 3[CH2-2-C6F4P(C6F 5)CH2]2-1,3}RhX]+ exclusively. The structure of [{(η5-C5Me4H)RhCl2} 2] has been determined by single-crystal X-ray diffraction.
