P. Leoni, E. Vichi, S. Lencioni
Jul 6, 2000
Citations
0
Influential Citations
14
Citations
Journal
Organometallics
Abstract
Methyl acrylate reacts with [Pd2(μ-PR2)(μ-PR2H)(PR2H)2]X (R = But; 1a, X = CF3SO3; 1b, X = BF4) to give, after CC insertion into the PH bonds of di-tert-butylphosphine, [Pd2(μ-PR2)(μ,η2-O2SOCF3)(η1-PR2R‘)2] (5a) or [Pd2(μ-PR2)(η2-PR2R‘)2] BF4 (5b) (R‘ = CH2CH2COOMe). The reaction of 1a with methyl methacrylate proceeds analogously, forming [Pd2(μ-PR2)(η2-PR2R‘ ‘)2]CF3SO3 (6) (R‘ ‘ = CH2CH(CH3)COOMe) as a mixture of diastereoisomers. The unsaturated [Pd2(μ-P)(P)2] core is stabilized by the coordination of the triflate anion (5a) or of the carbonyl groups of the functional phosphines (5b and 6). The weak Pd−O interactions in 5a and 5b are easily displaced by CO or p-tolylisonitrile, yielding [Pd2(μ-PBut2)(L)2{η1-PBut2(CH2CH2COOMe)}2]X (7a,b, L = CO; 8, L = CN−C6H4-p-Me, X = CF3SO3). The reaction of 5a with an excess of p-tolylisonitrile gives the new triangulo cluster Pd3(μ-PBut2)2(CN-C6H4-p-Me)5](CF3SO3)2, (9). The X-ray crystal and molecular structures of 5a and 9 are also reported.