title: Dinuclear (d(3)-d(3)) Diolate Complexes of Molybdenum and Tungsten. 2.(1) Derivatives of 2,2'-Methylenebis(6-tert-butyl-4-methylphenoxide). Direct Observation of the Conversion of Bridged to Chelate Isomers (M = Mo) and Reversible Carbon-Hydrogen Bond Oxidative Addition (M = W).
abstract: Hydrocarbon solutions of Mo(2)(NMe(2))(6) and 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (>/=2 equiv), HO&ndblwave;CH(2)&ndblwave;OH, yield Mo(2)(NMe(2))(2)(O&ndblwave;CH(2)&ndblwave;O)(2), I, which exists in bridged Ib and chelated Ic isomers. These are formed under kinetic control, and recrystallization allows the separation of Ib (orange cubes) from Ic (yellow cubes) both of which have been crystallographically characterized. In each there is an ethane-like O(2)NMo&tbd1;MoO(2)N core with Mo-Mo = 2.2 Å (average). In Ib the two O&ndblwave;CH(2)&ndblwave;O ligands span the Mo&tbd1;Mo bond yielding a molecule of C(2) symmetry. In Ic the molecule has near-C(2) symmetry in the solid state, but in solution there is either rapid rotation about the M&tbd1;M bond or the anti-rotamer is preferred. In benzene-d(6), Ib and Ic do not interconvert at 110 degrees C over a period of days. However, the addition of pyridine or acetonitrile causes the isomerization of Ib to Ic, thereby establishing that Ic is the thermodynamic isomer. The rate of conversion of Ib to Ic has been shown to be dependent on the square of the concentration of added pyridine: k(obs) = k[py](2). From the temperature dependence of k(obs), we determine DeltaH() = 19 (+/-1) kcal/mol and DeltaS() = -25 (+/-3) eu for the pyridine-promoted isomerization of Ib to Ic. The related reaction involving W(2)(NMe(2))(6) and HO&ndblwave;CH(2)&ndblwave;OH (>/=2 equiv) in hydrocarbon solvents at room temperature and below yields a dark brown crystalline compound, wherein C-H activation has occurred at one of the O&ndblwave;CH(2)&ndblwave;O diolate ligands, W(2)(&mgr;-H)(&mgr;-NMe(2))(NMe(2))(eta(2)-O&ndblwave;CH(2)&ndblwave;O)(eta(3)-O&ndblwave;CH&ndblwave;O)(HNMe(2)), 2. The W-W distance in 2 is 2.495(1) Å, consistent with a (W=W)(8+) core. Heating 2 in the solid-state under a dynamic vacuum leads to the elimination of HNMe(2) and the formation of 3, W(2)(NMe(2))(2)(eta(2)-O&ndblwave;CH(2)&ndblwave;O)(2), an analog of Ic. In benzene-d(6) the equilibrium involving 2 and 3 + HNMe(2) has been observed by (1)H NMR spectroscopy. The addition of pyridine to hydrocarbon solutions of 3 yields W(2)(&mgr;-H)(&mgr;-NMe(2))(eta(2)-O&ndblwave;CH(2)&ndblwave;O)(&mgr;(3)-O&ndblwave;CH&ndblwave;O)(NMe(2))(py), 4, which has been shown by single-crystal X-ray crystallography to be an analogue of 2. Studies of the addition of PMe(3) to toluene-d(8) solutions of 3 at low temperatures reveal that adduct formation occurs prior to C-H oxidative addition. For the equilibrium involving 4 and 3 + py in benzene-d(6), DeltaH degrees = 14 (+/-1) kcal/mol and DeltaS degrees = 22 (+/-3) eu.
authors.affiliation: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405.
authors.forename: Malcolm H.
authors.initials: MH
authors.lastname: Chisholm
authors.forename: Jui-Hsien
authors.initials: JH
authors.lastname: Huang
authors.forename: John C.
authors.initials: JC
authors.lastname: Huffman
authors.forename: Ivan P.
authors.initials: IP
authors.lastname: Parkin