Organometallic early transition metal

Mashima K, Nakayama Y and Nakamura A 1997 Recent trends in polymerization of a-olefins catalyzed by organometallic complexes of early transition metals Adv. Polym. Sc/. 133 1-54... 

Whereas CP2MX2 compounds are ubiquitous ia early transition-metal organometallic chemistry, the thorium analogues are rather unstable. 

Bis(cyclopentadienyl) complexes are central to the organometallic chemistry of the early transition metals and feature in applications such as alkene polymerization chemistry. Parallels can be drawn between a porphyrin ligand and two cyclopentadienyl ligands, in that they both contribute a 2— formal charge and exert a considerable steric influence on other ligands in the same molecule. Several of the metalloporphyrin complexes discussed below have bis(cyclopentadienyl) counterparts, and authors in some ca.ses have drawn quite detailed comparisons, although these discussions will not be repeated here. 

The last decade has seen the development of a rich and varied chemistry for or-ganometallic porphyrin complexes of the early transition metals (groups 3 and 4). However, there have been many fewer developments in the organometallic chemistry of the middle transition elements. Despite the paucity of its organometallic porphyrin compounds, molybdenum has played a very important role in... 

Mashima, K., Nakayama, Y. and Nakamura. A. Recent Trends in Polymerization of a-Oleftm Catalyzed by Organometallic Complexes of Early Transition Metals. Vol. 133, pp. 1-52. 

Organometallic complexes of the /-elements have been reported that will perform both intra-and intermolecular hydroamination reactions of alkenes and alkynes, although these lie outside of the scope of this review.149-155 Early transition metal catalysts are not very common, although a number of organometallic systems exist.156-158 In these and other cases, the intermediacy of a metal imido complex LnM=NR was proposed.159,160 Such a species has recently been isolated (53) and used as a direct catalyst precursor for N-H addition to alkynes and allenes (Scheme 35).161,162... 

In this contribution, we review the mechanism of polymerization and oligomerization involving early transition metals, taking as our basis recent results in advanced organometallic chemistry. First of all, some recent examples of the previous reviews concerning the Ziegler-Natta polymerization are cited [1-10]. Then, relevant new reports are surveyed in a systematic fashion. 

General Features of Organometallic Complexes of Early Transition Metals... 

The molecular design of stereospecific homogeneous catalysts for polymerization and oligomerization has now reached a practical stage, which is the result of the rapid developments in early transition metal organometallic chemistry in this decade. In fact, Exxon and Dow are already producing polyethylene commercially with the help of metallocene catalysts. Compared to the polymerization of a-olefins, the polymerization of polar vinyl, alkynyl and cyclic monomers seems to be less developed. 

Dioxygen Activation by Organometallics of Early Transition Metals K.H. Theopold. 17... 

Keywords Organometallics Dioxygen Early transition metals Oxygen atom transfer... 

Tejel C, Ciriano MA (2007) Catalysis and Organometallic Chemistry of Rhodium and Iridium in the Oxidation of Organic Substrates. 22 97-124 Tekavec TN, Louie J (2006) Transition Metal-Catalyzed Reactions Using N-Heterocyclic Carbene Ligands (Besides Pd- and Ru-Catalyzed Reactions). 21 159-192 Theopold KH (2007) Dioxygen Activation by Organometallics of Early Transition Metals. 22 17-37... 

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