Acyclic alkanes ethane

Having set out the properties of tantalum and zirconium hydride toward C-H bond activation of alkanes we now describe the catalytic hydrogenolysis of C-C bonds. It was previously shown in the laboratory that supported-hydrides of group 4 metals, and particularly of zirconium, catalyze the hydrogenolysis of alkanes [21] and even polyethylene [5] into an ultimate composition of methane and ethane. However, to our initial surprise, these zirconium hydrides did not cleave ethane. (=SiO)2Ta-H also catalyzes the hydrogenolysis of acyclic alkanes such as propane, butane, isobutane and neopentane. But, unlike the group 4 metals, it can also cleave ethane [10], Figure 3.7 illustrates this difference of behavior between (=SiO)2Ta(H) and [(=SiO)(4.j,)Zr(H) ], x= or 2). With Ta, propane is completely transformed into methane by successive reactions, while with Zr only equimolar amounts of methane and ethane are obtained. 

In the presence of an acyclic alkane, 3 catalyzes at moderate temperature (25-200 °C) the metathesis reaction, leading to the formation of heavier and lower homolog alkanes by simultaneous breaking and formation of C-H and C-C bonds. For example, propane is transformed, even at 25 °C into a quasi-equimolar mixture of ethane and butanes (n- and iso-mixture) as well as methane and pentanes, in lower quantities. Lower and heavier homologs are also obtained starting from... 

Alkane metathesis was first reported in 1997 [84]. Acyclic alkanes, with the exception of methane, in contact with a silica supported tantalum hydride ](=SiO)2TaH] were transformed into their lower and higher homologues (for instance, ethane was transformed into methane and propane). Later, the reverse reaction was also reported [85]. Taking into accountthe high electrophilic character ofa tantalum(III) species, two mechanistic hypotheses were then envisaged (i) successive oxidative addition/reductive elimination steps and (ii) o-bond metathesis. Further work has shown that aLkyhdene hydrides are critical intermediates, and that carbon-carbon... 

Structures for the two simplest acyclic alkanes were given in Chapter 1. Methane, CH4, has a single carbon atom, and ethane, CH3CH3, has two. All C atoms in an alkane are surrounded by four groups, making them sp hybridized and tetrahedral, and all bond angles are 109.5°. 

Alkanes. The saturated open-chain (acyclic) hydrocarbons (C H2 +2) have names ending in -ane. The first four members have the trivial names methane (CH4), ethane (CH3CH3 or C2H5), propane (C3H8), and butane (C4Hjo). For the remainder of the alkanes, the first portion of the name... 

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