A multinuclear NMR study of [Pt0(PPh3)2(alkene)] compounds containing asymmetric olefins.
The 1H, 13C, 31P, and 195Pt NMR spectra of [Pt0(PPh3)2(eta-ABC(1) = C(2)XY)] compounds (ABC(1)= C(2)XY (1) A = B = X = Y = H; (3) A = B = X = H, Y = CN; (4) A = H, B = p-NO2-Ph, X = COOCH3, Y = CN; (5) A = H, B = Ph, X = COOCH3, Y = CN; (6) A = H, B = Ph, X = Y = CN; (7) A = H, B = OEt, X = Y = CN), where X and Y are electronacceptor substituents, and the 1H spectrum of [Pt0(PPh3)2(eta2-C60)] (2) are reported together with extended analyses and assignments, based also on the ring current effect of the olefin phenyl in (4-6). Deviations from first order in the 13C spectra allowed the determination of the relative signs of the coupling constants J(P(1), C) and J(P(2), C) of the alkene and of the triphenylphosphine carbons. Best fit simulation of the phosphine C ipso spectrum provided also the 13C isotopic shift on phosphorus for (1). These compounds are characterised by strong differences between the two platinum-phosphorus coupling constants in the case of asymmetric olefins (3-7). The chemical shifts of alkene C(1) and C(2) indicate notable polarisation of the olefin after complexation, while the 1J(Pt, C(1)) and 1J(Pt, C(2)) values are in agreement with a stronger interaction of Pt with C(1) than with C(2). These findings together with the trend of 195Pt chemical shifts confirm the important role played by back-donation in the bonding of platinum(0)-olefin compounds.
Asaro
F
F
Dipartimento di Scienze Chimiche, Unirersità di Trieste, Italy. asaro@dsch.univ.trieste.it
Lenarda
M
M
Pellizer
G
G
Storaro
L
L
D000475:Alkenes / Q000737:chemistry*; D008968:Molecular Conformation; D019906:Nuclear Magnetic Resonance, Biomolecular; D017671:Platinum Compounds / Q000737:chemistry*
D000475:Alkenes; D017671:Platinum Compounds