Methyl acrylate reacts with [Pd-2(mu-PR2)(mu-PR2H)(PR2H)(2)]X (R = Bu-t; 1a, X = CF3SO3; 1b, X = BF4) to give, after CC insertion into the PH bonds of di-tert-butylphosphine, [Pd-2-(mu-PR2)(mu,eta(2)-O2SOCF3)(eta(1)-PR2R')(2)] (5a) or [Pd2(mu-PR2)(eta(2)-PR2R')(2)] BF4 (5b) (R' = CH2CH2-COOMe). The reaction of 1a with methyl methacrylate proceeds analogously, forming [Pd-2-(mu-PR2)(eta(2)-PR2R ")(2)]CF3SO3 (6) (R " = CH2CH(CH3)COOMe) as a mixture of diastereoisomers. The unsaturated [Pd-2(mu-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 [Pd-2(mu-PBu2t)(L) (2){eta(1)-PBu2t(CH2CH2COOMe)}(2)]X (7a,b, L = CO; 8, L = CN-C6H4-p-Me, X = CF3-SO3). The reaction of 5a with an excess of p-tolylisonitrile gives the new triangulo cluster [Pd-3(mu-PBu2t)(2)(CN-C6H4-p-Me)(5)](CF3SO3)(2), (9) The X-ray crystal and molecular structures of 5a and 9 are also reported.

Hemilabile phosphines by methyl acrylate insertion into the P-H bonds of palladium(I)-coordinated secondary phosphines. Labile anion (X = OTf) vs PO-chelate coordination (X = BF4) in Pd2(mu-PR2)(PR2R ')2(X) (R = Bu-t, R ' = CH2CH2COOMe; X = OTf, BF4)

LEONI, PIERO;PASQUALI, MARCO;
2000-01-01

Abstract

Methyl acrylate reacts with [Pd-2(mu-PR2)(mu-PR2H)(PR2H)(2)]X (R = Bu-t; 1a, X = CF3SO3; 1b, X = BF4) to give, after CC insertion into the PH bonds of di-tert-butylphosphine, [Pd-2-(mu-PR2)(mu,eta(2)-O2SOCF3)(eta(1)-PR2R')(2)] (5a) or [Pd2(mu-PR2)(eta(2)-PR2R')(2)] BF4 (5b) (R' = CH2CH2-COOMe). The reaction of 1a with methyl methacrylate proceeds analogously, forming [Pd-2-(mu-PR2)(eta(2)-PR2R ")(2)]CF3SO3 (6) (R " = CH2CH(CH3)COOMe) as a mixture of diastereoisomers. The unsaturated [Pd-2(mu-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 [Pd-2(mu-PBu2t)(L) (2){eta(1)-PBu2t(CH2CH2COOMe)}(2)]X (7a,b, L = CO; 8, L = CN-C6H4-p-Me, X = CF3-SO3). The reaction of 5a with an excess of p-tolylisonitrile gives the new triangulo cluster [Pd-3(mu-PBu2t)(2)(CN-C6H4-p-Me)(5)](CF3SO3)(2), (9) The X-ray crystal and molecular structures of 5a and 9 are also reported.
2000
Leoni, Piero; Vichi, E; Lencioni, S; Pasquali, Marco; Chiarentin, E; Albinati, A.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/190675
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