Late-transition metals

Arrington C A, Morse M D and Doverstal M 1995 Spectroscopy of mixed early-late transition metal diatomics ScNi, YPd, and ZrCo J. Chem. Rhys. 102 1895... 

A variety of complexes of the thionyl imide anion [NSO] with both early and late transition-metal complexes have been prepared and structurally characterized. Since both ionic and covalent derivatives of this anion are readily prepared, e.g., K[NSO], McsMNSO (M = Si, Sn) or Hg(NSO)2, metathetical reactions of these reagents with transition-metal halide complexes represent the most general synthetic method for the preparation of these complexes (Eq. 7.10 and 7.11). ... 

Tp )FeMe] [Tp = phenyltris(3-tert-butylpyrazol-l-yl)borate] (98JA10561) and [(> -Tp )FeR] [Tp = hydrotris(3,5-diisopropylpyrazol-l-yl)borate R = Ft, CH2CHCH2, CH2T0I-P] [98JCS(CC)973, 99JCS(CC)417] are prepared by methods similar to those described for the similar non-transition and late-transition metal alkyls. 

Late Transition Metal-catalyzed Polymerization of Ethylene... 

The discussion about the mechanism of the dehydrogenative polymerization reaction has not yet been completed. However, the reaction mechanism seems to be strongly influenced by the specific random conditions that apply for each particular system. Presumably with late transition metals a silylene mechanism is more appropriate. It may be a matter of the steric constraints of the system to shift the reaction towards a-bond metathesis. 

Kinetic studies using 1,9-decadiene and 1,5-hexadiene in comparison widi catalyst 14 and catalyst 12 demonstrate an order-of-magnitude difference in their rates of polymerization, widi 14 being the faster of the two.12 Furdier, this study shows diat different products are produced when die two catalysts are reacted widi 1,5-hexadiene. Catalyst 14 generates principally lineal" polymer with the small amount of cyclics normally observed in step condensation chemistry, while 12 produces only small amounts of linear oligomers widi die major product being cyclics such as 1,5-cyclooctadiene.12 Catalyst 12, a late transition metal benzylidene (carbene), has vastly different steric and electronic factors compared to catalyst 14, an early transition metal alkylidene. Since die results were observed after extended reaction time periods and no catalyst quenching or kinetic product isolation was performed, this anomaly is attributed to mechanistic differences between diese two catalysts under identical reaction conditions. 

Functionalized polyethylene would be of great industrial importance, and if synthetic methods to control the microstructure of functionalized polymers using transition-metal-based catalysis are developed, it would significantly broaden the utility and range of properties of this class of polymers. Recent progress in the field of late transition metal chemistry, such as Brookliart s use of nickel-based diimine catalysts, has enabled the copolymerization of ethylene with functional a-olefins.29 However, these systems incorporate functionalized olefins randomly and with limited quantity (mol percent) into the polymer backbone. 

C. Amidinate and guanidinate complexes of the middle and late transition metals... 

Tullock C.W. et al.. Polyethylene and elastomeric polypropylene using alumina-supported bis(arene) titanium, zirconium, and hafnium catalysts, J. Polym. Sci, Part A, Polym. Chem., 27, 3063, 1989. Mueller G. and Rieger R., Propene based thermoplastic elastomers by early and late transition metal catalysis. Prog. Polym. Sci., 27, 815, 2002. 

The vast majority of phosphine/phosphite-substituted products involve F-ligand ligation at late transition metals. In contrast, phosphite ligands displaced rhenium-coordinated CO or acetylene in [RePt3(/i-dppm)3(CO)3(L)l", - which are the... 

Research into cluster catalysis has been driven by both intrinsic interest and utilitarian potential. Catalysis involving "very mixed -metal clusters is of particular interest as many established heterogeneously catalyzed processes couple mid and late transition metals (e.g., hydrodesulfurization and petroleum reforming). Attempts to model catalytic transformations arc summarized in Section II.F.I., while the use of "very mixed -metal clusters as homogeneous and heterogeneous catalysis precursors are discussed in Sections I1.F.2. and I1.F.3., respectively. The general area of mixed-metal cluster catalysis has been summarized in excellent reviews by Braunstein and Rose while the tabulated results are intended to be comprehensive in scope, the discussion below focuses on the more recent results. 

Michalak A, Ziegler T (2005) Late Transition Metal as Homo- and Co-Polymerization Catalysts. 12 145-186... 

This highhght examines several new hybrid layered structures in the hetero-metallic perrhenate and vanadate families, whereby the late transition-metals are incorporated and their roles probed in the structures of layered solids. From these two families, new structural principles have emerged that not only help us understand key stractural features and correcdy forecast new compositions, but equally, have yielded many surprises (chirality, reduced phases) that show some of the most exciting chemistry is still waiting to be discovered or even imagined ... 

The late transition metals, either Co or Ni, bond to four apical oxygen atoms of two vertex-shared 5 units (Fig. 17.9a), two each to layers both above and below, and also bond to two bridging pyrazine ligands in a trans fashion. The al-... 

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