Electron-poor 2,3-dihydro-1,3-diborolyl complexes of iron and ruthenium: Synthesis, reactivity, and crystal and electronic structures of an iron sandwich complex

The addition product of sodium hydride and the 2,3-dihydro-1,3-diborole (CiPr)(2)(BEt)(2)CHMe (3c) reacted with [{(C(5)Me(5))FeCl}(x)] to produce the green sandwich complex [(C(5)Me(5))Fe{eta(5)-(CiPr)(2)(BEt)(2)CMe}] (2c), which formally contains 16 valence electrons (VE). Complex 2c has unexpected structural properties in the solid state: the 1,3-diborolyl ring is extremely folded (41 degrees), and the Fe-C2 distance is short (1.90 Angstrom). Analogously, violet Ru complexes 4 a,c,d were obtained from 3a,c, NaH or tBuLi, and [{(C(5)Me(5))RuCl}(4)]. With the less bulky heterocycles 3b,e the new 30 VE triple-decker complexes [(C(5)Me(5))Ru{rho,eta(5)- (CR(1))(2)(BR(2))(2)CMe}RuH(C(5)Me(5))] (5b,e) were formed, which contain a Ru-H bond. Cyclic voltammetric studies revealed the existence of stable anions 2c(-) and 4d(-) formed by reversible one-electron reduction at -1.26 and -1.40 V, respectively (vs. SCE). The red-brown anions were further characterized by ESR spectroscopy following stepwise reduction of the neutral species with potassium in THE Addition of CO to 4a and 4d led to formation of the monocarbonyl complexes [(C(5)Me(5))Ru(CO){eta(5)-(CR(1))(2-) (BR(2))(2)CMe}] (6a,d), and 6d was characterized by X-ray structure analysis. The heterocycle in 6d is less folded (19 degrees) than in 2c. Its CO ligand causes a 28.5 degrees tilt of the cyclic ligands. Reaction of CO with 2c yielded a red product of unknown structure. The electronic structure of 2 was studied by EH-MO theory, which revealed a unique bonding in the sandwich. The sigma electron density of the B-C bonds participates in the bonding to the iron atom; this demonstrates that the number of bonding electrons is the same as in ferrocene. Thus, the complexes 2 actually have 18 VE.