| Abstract
| - Treatment of W(NPh)(o-(Me3SiN)2C6H4)(py)2 with 2 equiv of RC(O)H [R = Ph, tBu] quickly generates W(NPh)(o-(Me3SiN)2C6H4)(OCH2R)(OCH(R)-o-C5H4N), which results from coupling a pyridine ligand to the aldehyde substrate via C−H activation of the pyridine. Labeling studies have been performed, and numerous substrates have been tried, in an attempt to understand this unusual transformation.
- The reactivity of W(NPh)(o-(Me3SiN)2C6H4)(py)2 and W(NPh)(o-(Me3SiN)2C6H4)(pic)2 (py = pyridine; pic = 4-picoline)with unsaturated substrates has been investigated. Treatment of W(NPh)(o-(Me3SiN)2C6H4)(py)2 with diphenylacetyleneor 2,3-dimethyl-1,3-butadiene generates W(NPh)(o-(Me3SiN)2C6H4)(η2-PhC⋮CPh) (1) and W(NPh)(o-(Me3SiN)2C6H4)(η4-CH2C(Me)C(Me)CH2) (3), respectively, while the addition of ethylene to W(NPh)(o-(Me3SiN)2C6H4)(py)2generates the known metallacycle W(NPh)(o-(Me3SiN)2C6H4)(CH2CH2CH2CH2). The addition of 2 equiv of acetoneto W(NPh)(o-(Me3SiN)2C6H4)(pic)2 provides the azaoxymetallacycle W(NPh)(o-(Me3SiN)2C6H4)(OCH(Me)2)(OC(Me)2-o-C5H3N-p-Me) (4), the result of acetone insertion into the ortho C−H bond of picoline. Similarily, the addition of2 equiv of RC(O)H [R = Ph, tBu] to W(NPh)(o-(Me3SiN)2C6H4)(py)2 generates W(NPh)(o-(Me3SiN)2C6H4)(OCH2R)(OCH(R)-o-C5H4N) [R = Ph, 5; tBu, 6]. In contrast, reaction between W(NPh)(o-(Me3SiN)2C6H4)(py)2 and 2-pyridinecarboxaldehyde yields the diolate W(NPh)(o-(Me3SiN)2C6H4)(OCH(C5H4N)CH(C5H4N)O) (7). The synthesis of W(NPh)(o-(Me3SiN)2C6H4)(PMe3)(py)(η2-OC(H)C6H4-p-Me) (9), formed by the addition of p-tolualdehyde to a mixture ofW(NPh)(o-(Me3SiN)2C6H4)(py)2 and PMe3, suggests that an η2-aldehyde intermediate is involved in the formationof the azaoxymetallacycle, while the isolation of W(NPh)(o-(Me3SiN)2C6H4)(Cl)(OC(Me)(CMe3)-o-C5H4N) (10), formedby the reaction of pinacolone with W(NPh)(o-(Me3SiN)2C6H4)(py)2, in the presence of adventitious CH2Cl2, suggeststhat the reaction proceeds via the hydride W(NPh)(o-(Me3SiN)2C6H4)(H)(OC(Me)(CMe3)-o-C5H4N).
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