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With chromium(II) supported on silica, at T &gt; 150 °C olefins undergo growth/degradation/metathesis reactions by addition/elimination of even and uneven chain fragments including Ci. Simultaneously, catalytic double bond isomerization and C-rearrangements to methyl branched olefins occur. One mechanism is proposed for all these reactions via a pseudo-tetrahedral MC 3  intermediate. Polyethylene synthesis at lower temperatures may follow the same way. For growth/degradation/metathesis the formation of a metal carbene unit is postulated as a characteristic, step; in case of ethylene, &gt;Cr=CH 2  will be formed as a precursor of the final CH 4  (resulting from a secondary reaction with support hydrogen).

zeitschrift für naturforschung b

Oberflächenverbindungen von Übergangsmetallen, XXII [1]. Die Umsetzung von Oberflächen-Chrom(II) auf Silicagel mit Olefinen bei höherer Temperatur. - Zum Mechanismus von Aufbau-, Abbau-, Metathese- und Isomerisierungs-Reaktionen an koordinativ ungesättigten Oberflächen-Metallionen / Surface Compounds of Transition Metal, XXII [1]. The Reaction of Surface Chromium(II) on Silica with Olefins at Higher Temperature. - A Contribution to the Mechanism of Growth, Degradation, Metathesis and Isomerization on Coordinatively Unsaturated Surface Metal Ions