The preparation and spectroscopic properties are described of some platinum(II) complexes having a hydride ligand cis or trans to an sp3 carbon, viz. trans-PtH(YCN)(PPh3)2 and cis-PtH(YCN)(L-L) with YCN = C2H4CN, n-C3H6CN, o-CH2C6H4CN and L-L = bis(diphenylphosphino)-ethene or -ethane. The complexes trans-PtH(YCN)(PPh3)2 can add a fifth ligand in solution; the resulting five-coordinate complex was observed by 31P NMR in the case of PtH(C3H6CN)(PPh3)3. Insertion of olefin (ethen, 1-cyanoethene, norbornadiene, allen) into the Pt-H bond of the trans-hydrido complexes occurs to give cis-dialkyl complexes, but the cis-hydrido complexes are unreactive. The mechanism of insertion is discussed in terms of the kinetics and the geometries of reactants and products.
Hydridocyanoalkyl complexes of platinum(II). Insertion of olefins into the Pt-H bond
ROS, RENZO;MICHELIN, RINO;
1979
Abstract
The preparation and spectroscopic properties are described of some platinum(II) complexes having a hydride ligand cis or trans to an sp3 carbon, viz. trans-PtH(YCN)(PPh3)2 and cis-PtH(YCN)(L-L) with YCN = C2H4CN, n-C3H6CN, o-CH2C6H4CN and L-L = bis(diphenylphosphino)-ethene or -ethane. The complexes trans-PtH(YCN)(PPh3)2 can add a fifth ligand in solution; the resulting five-coordinate complex was observed by 31P NMR in the case of PtH(C3H6CN)(PPh3)3. Insertion of olefin (ethen, 1-cyanoethene, norbornadiene, allen) into the Pt-H bond of the trans-hydrido complexes occurs to give cis-dialkyl complexes, but the cis-hydrido complexes are unreactive. The mechanism of insertion is discussed in terms of the kinetics and the geometries of reactants and products.Pubblicazioni consigliate
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