Complexes platinum hydride

Hydrogen cyanide reactions catalysts, 6,296 Hydrogen ligands, 2, 689-711 Hydrogenolysis platinum hydride complexes synthesis, 5, 359 Hydrogen peroxide catalytic oxidation, 6, 332, 334 hydrocarbon oxidation iron catalysts, 6, 379 reduction... 

Fig. 11.24. Positive-ion ESI spectrum of a cationic dinuclear platinum hydride complex from dichloromethane solution. The insets compare experimental and theoretical isotopic patterns. By courtesy of P. Hofmann, University of Heidelberg.

Stern showed rather conclusively that the palladium does not depart to leave a carbonium ion but that both hydride migration and collapse to an aldehyde proceed simultaneously. The removal of the /3 hydrogen in a complexes by the heavier Group VIII metals has been documented. Thus Chatt and Shaw (63) showed that a platinum hydride complex could undergo the reversible addition of ethylene ... 

These platinum hydride complexes immediately alerted us to the possibility of preparing other similar complexes. Within a decade a great number were obtained from the Group VIII metals (49) and even now the series is being extended to include the early transition metal groups (S). 

Coordinated 2,3-dihydrothiophene (DHT) in a platinum hydride complex (32) rearranges slowly, by inserting into the M—H bond, to give 33. A... 

Scheme 2. Syntheses of platinum hydride complexes containing dppe.

The s-electron density at the nucleus is affected by the effective nuclear charge. An increase in the latter quantity on the metal atom would increase Jm-h- The large value for JPt H in platinum-hydride complexes has been attributed to the effective nuclear charge of the platinum 239a) and the striking increase in Jm-h with increasing atomic number for the... 

Platinum hydride complexes were prepared by the following reaction (16) ... 

Hydride complexes of platinum have received considerable study since the preparation of PtHCl(PEt3)2- Spectroscopic studies by NMR techniques have been widely used because of the structural information which can be obtained from coupling constant data to Pt and other nuclei. Platinum is widely used as a heterogeneous catalyst, and vibrational studies on platinum hydride complexes have been useful for comparison of a hydrogen atom bonded to a single platinum with that bonded to a surface. Complexes of platinum have been used to catalyze hydrogenation, hydrosilylation and isomerization reactions with alkenes and alkynes, as well as H/D exchange reactions on alkanes. Hydride complexes are frequently proposed as intermediates in these reactions, and the pathways related to the known chemistry of hydride complexes. 

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