196512-93-3Relevant academic research and scientific papers
Synthesis, structure, and reactivity of 2-phosphabenzyne-zirconocene dimers
Rosa, Patrick,Floch, Pascal Le,Ricard, Louis,Mathey, Fran?ois
, p. 9417 - 9423 (2007/10/03)
The extrusion of methane from (2-phosphininyl)(methyl) zirconocenes 3a-c at 80°C in benzene affords the corresponding 2-phosphabenzyne-zirconocene dimers 4a-c, one of which has been characterized by X-ray crystal structure analysis. The parameters of the C-C-Zr three-membered ring are exactly similar to those found in the 2-benzyne-zirconocene complex: C-C, 1.361(2); C-Zr, 2.238 and 2.250(2) A?. The P-Zr distances are normal at 2.6857(5) and 2.6922(5) A?. The reaction of these 2-phosphabenzyne complexes with acetonitrile, Ph3P=S, (diphenylphosphino)- and (trimethylsilyl)alkynes, aldehydes, and (+)-camphor have been investigated. In all cases, an insertion into the C2-Zr bond is observed. Hydrolysis of the intermediate zirconacycles thus obtained yielded several new 2-functional phosphinines, including a thiol (6), a vinylphosphine (8), two secondary alcohols (14 and 15), and an homochiral phosphinine-substituted alcohol (17). The regiospecificity of the insertion is ascribed to the huge concentration of negative charge at the α-position of the phosphinine ring.
