Abstract
Reaction of NaRe(CO)5 with Ph3CPF6 affords Re(CO)4(η3-CPh3) (1). Complex 1 reacts readily with CO at room temperature to give the •Re(CO)5 radical, which forms Re2(CO)10 in the absence of trapping agents. The radical reacts with CCl4 to give Re(CO)5Cl and with Fe(CO)5 to give Re2Fe(CO)14 (2). Compounds 1 and 2 have been structurally characterized. Compound 1 crystallizes in the triclinic space group P1 with lattice parameters a = 11.062 (2) Å, b = 11.383 (1) Å, c = 17.961 (3) Å, α = 104.62 (1)°, γ = 94.77 (2)°, and γ = 98.52 (1)°. The final R value was 3.7%. The structure shows a Re(CO)4 moiety coordinated to the central carbon of the triphenylmethyl unit and two carbons of one phenyl ring. Complex 2 crystallizes in the monoclinic space group C2/m with lattice parameters a = 12.083 (3) Å, b = 14.705 (4) Å, c = 11.822 (3) Å, and β = 97.43 (2)°. The final R value was 3.4%. The structure shows a linear Re-Fe-Re array.