Synthesis, structure, and reactivity of fluorous phosphorus/carbon/phosphorus pincer ligands and metal complexes

Reactions of the diphosphine 1,3-C6H4(CH2PH2)2 and fluorous alkenes H2C=CHR(fn)(R(fn)=(CF2)(n-1)CF3; n = 6, 8) at 75 degrees C in the presence of AIBN give the title ligands 1,3-C6H4(CH2P(CH2CH2R(fn))2)2(3-R(fn)) and byproducts 1,3-C6H4(CH3)(CH2P(CH2CH2R(fn))2)(4-R(fn)) in 1 : 3 to 1 : 5 ratios. Workups give -R(fn) in 4--17% yields. Similar results are obtained photochemically. Reaction of 1,3-C6H4(CH2Br)2 and HP(CH2CH2R(f8))2 (5) at 80 degrees C (neat, 1 : 2 mol ratio) gives instead of simple substitution the metacyclophane [1,3-C6H4(CH2P(CH2CH2R(f8))2 CH2-1,3-C(6)H(4)CH(2)P[lower bond 1 end](CH2CH2R(f8))2C[upper bond 1 end]H2](2+)2Br-, which upon treatment with LiAlH(4) yields 3-R(f8)(20%), 4-R(f8), and other products. Efforts to better access 3-R(f8), either by altering stoichiometry or using various combinations of the phosphine borane (H3B)PH(CH2CH2R(f8))2 and base, are unsuccessful. Reactions of 3-R(fn) with Pd(O2CCF3)2 and [IrCl(COE)2]2(COE=cyclooctene) give the palladium and iridium pincer complexes (2,6,1-C6H3(CH2 P(CH2CH2R(fn))(2)(2)Pd(O2CCF3)(10-R(fn); 80-90%) and (2,6,1-C6H3(CH2P(CH2CH2R(f8))2)2)Ir(Cl)(H)(11-R(f8); 29%), which exhibit CF3C6F(11)/toluene partition coefficients of >96 : <4. The crystal structure of 10-R(f8) shows CH2CH2R(f8) groups with all-anti conformations that extend in parallel above and below the palladium square plane to create fluorous lattice domains. NMR monitoring shows a precursor to 11-R(f8) that is believed to be a COE adduct.