M. Ogasawara et al., CHARACTERIZATION AND REACTIVITY OF AN UNPRECEDENTED UNSATURATED ZERO-VALENT RUTHENIUM SPECIES - ISOLABLE, YET HIGHLY REACTIVE, Journal of the American Chemical Society, 118(42), 1996, pp. 10189-10199
Magnesium reduction of cis,cis,trans-RuCl2(CO)(2)L(2) (L = P(t)Bu(2)Me
) yields isolable Ru(CO)(2)L(2), shown by solution spectroscopies and
X-ray diffraction to have trans phosphines but cis carbonyls, in a non
planar structure which resembles a trigonal bipyramid with one equator
ial ligand missing. This unusual geometric structure is traced by ab i
nitio (MP2) study to enhanced back-donation to CO by zero-valent Ru. T
his molecule reacts in time of mixing to add CO, MeNC, O-2, CS2, C2H4,
or PhC=CPh. Rapid oxidative addition occurs with H-2, HCl, Cl-2, and
PhC=CH. Oxidative addition is slower with MeCl, Me(3)SiH, and MeOH, wh
ich leads to more complicated reaction schemes. Reaction with PPh(2)H
gives not oxidative addition but addition and displacement, yielding R
u(CO)(2)-(PPh(2)H)(2)(P(t)Bu(2)Me) and equimolar free P(t)Bu(2)Me. Mag
nesium reduction of cis,cis,trans-RuCl2(CO)(2)L'(2) proceeds analogous
ly for L' = (PPr3)-Pr-t, but for L' = PPh(3), decomposition and ligand
scavenging give Ru(CO)(2)(PPh(3))(3). Reduction of cis,trans-RuCl2(CO
)(CNMe)L(2) gives the product of oxidative addition of a (t)Bu C-H bon
d: RuH(CO)(CNMe)-[eta(2)-P(CMe(2)CH(2))(t)BuMe]L, showing the influenc
e of electron density at unsaturated Ru(O) on its persistence.