The commercially available borane tris(pentafluorophenyl)borane, B(C(6)F(5))(3), is an effective catalyst for the dehydrogenative silation of alcohols using a variety of silanes, R(3)SiH, R(2)SiH(2), and R(2)R'SiH. Generally, the reactions occur in a convenient time frame at room temperature using 2 mol % of the borane and are clean and high yielding, with dihydrogen as the only byproduct. Primary aliphatic alcohols are silated cleanly but slowly, with reaction times ranging from 20 to 144 h. Faster reaction times can be achieved by increasing the catalyst loading to 8 mol % or by heating the reaction to approximately 60 degrees C. Secondary and tertiary alcohols react more rapidly, with most reactions being complete in 0.5-2 h. The reaction is tolerant of many functional groups including C=C, C&tbd1;C, -Br, aliphatic ketones, C(O)OR, lactones, furans, OBn, OMe, and NO(2); examples of each are given. Using the phenolic substrate 2,4,6-trimethylphenol, a number of different silanes were tested. Only the most bulky silanes (Bn(3)SiH and Pr(i)()(3)SiH) were not reactive under these conditions. The selectivity of the silation reactions are roughly governed by the relative basicity of the alcohols (and other functions in the molecule) with more basic groups being selectively silated. These observations are rationalized on the basis of a mechanism that invokes borane activation of the silane by hydride abstraction. The resulting intermediate silylium/hydridoborate ion pair then reacts with alcohols to give the observed silyl ether and dihydrogen products.

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The temperature dependence of the solid-state magnetic susceptibility for the paramagnetic V(I) complexes trans-(CpV)2(μ-η6:η6-C6H6) (1) and CpV(η6-C6H6) (2) has been investigated. Complex 1 obeys the Curie−Weiss law over the temperature range 10−300 K with μeff = 4.81 μB and ϑ = −18.8 K. The high-temperature moment is consistent with the presence of a total of four unpaired electrons derived from two low-spin V(I) d4 metal centers in an S = 2 configuration. However, at ca. 9 K the magnetic susceptibility displays a broad maximum. This magnetic behavior may be modeled over the full temperature range (4−300 K) using the Heisenberg intracluster magnetic exchange expression for an S 1 = S 2 = 1 system with g = 2.37, ϑ = −12.3 K, and J = −2.64 cm-1. Complex 2 obeys the Curie−Weiss law over the temperature range 5−300 K, with μeff = 2.86 μB and ϑ = −5.0 K. The X-ray structure of 2 (P21/a, a = 10.7842(4) Å, b = 7.8233(4) Å, c = 11.2017(5) Å, β = 113.830(2)° at 150 K, Z = 4) has been determined. Crystals of 2 undergo a reversible phase transition to a new monoclinic cell with a ‘ ≈ (a + c)/2, b ‘ ≈ b, c ‘ ≈ (c − a)/2 over the temperature range 290−270 K.

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