Metal complexation lanthanide

The insertion of metal fragments into hydrocarbon bonds is now a well-established phenomenon. While published research in this field has shown some decrease during the early 1990s, several excellent summaries of the last decade s pioneering studies have now become available. Most notable is Selective Hydrocarbon Activation, which features chapters on activation by electrophilic transition-metal complexes, lanthanide complexes, gas-phase ions, metal atoms, and others. Several other review articles of interest may be found in the introduction to this chapter. 

Carbon monoxide [630-08-0] (qv), CO, the most important 7T-acceptor ligand, forms a host of neutral, anionic, and cationic transition-metal complexes. There is at least one known type of carbonyl derivative for every transition metal, as well as evidence supporting the existence of the carbonyls of some lanthanides (qv) and actinides (1) (see AcTINIDES AND THANSACTINIDES COORDINATION COMPOUNDS). 

Different chiral transition- and lanthanide-metal complexes can catalyze the cycloaddition reaction of unactivated and activated aldehydes with especially activated... 

Different main-group-, transition- and lanthanide-metal complexes can catalyze the cycloaddition reaction of activated aldehydes with activated and non-activated dienes. The chiral metal complexes which can catalyze these reactions include complexes which enable substrates to coordinate in a mono- or bidentate fashion. 

Adenosine-5 -monophosphate lanthanide complexes NMR, 3,1104 Adenosine phosphates metal complexes, 2, 977 6, 445 Adenosine 5 -triphosphate... 

Aminopyridinato ligands form a special class of anionic ligands in which an aromatic ring is part of an amidinate system. These ligands have frequently been employed in early transition metal and lanthanide coordination chemistry. Their diverse and interesting chemistry has been described in detail by Kempe et al. ° and will thus be covered here only briefly. Typical reaction pathways leading to titanium aminopyridinato complexes are outlined in Scheme 169. Metathetical as well as salt-free routes have been developed. 

Blasse G (1976) The Influence of Charge-Transfer and Rydberg States on the Luminescence Properties of Lanthanides and Actinides. 26 43-79 Blasse G (1980) The Luminescence of Closed-Shell Transition Metal-Complexes. New Developments. 42 1-41... 

Busch DH (2005) First Considerations Principles, Classification, and History. 249 in press Bussiere G, Beaulac R, Belisle H, Lescop C, Luneau D, Rey P, Reber C (2004) Excited States and Optical Spectroscopy of Nitronyl Nitroxides and Their Lanthanide and Transition Metal Complexes. 241 97-118 Cadierno V, see Majoral J-P (2002) 220 53-77 Camara M, see Chhabra SR (2005) 240 279-315 Caminade A-M, see Majoral J-P (2003) 223 111-159 CantriU SJ, see Arico F (2005) 249 in press... 

Bray KL (2001) High Pressure Probes of Electronic Structure and Luminescence Properties of Transition Metal and Lanthanide Systems. 213 1 - 94 Bunz UHF (1999) Carbon-Rich Molecular Objects from Multiply Ethynylated rr-Complexes. 201 131-161... 

The PMRs of several triscyclopentadienyl-lanthanide metal complexes of cyclohexyl isocyanide (C5H5)3MCNCgH, (M = Pr, Nd, Ho, Tm, Yb) are reported 159, 160). 

The proposed mechanism for the metallocene complexes of Group 5 metals and lanthanides involves the coordination of alkene to the metal hydride (51), followed... 

Metal complexes of lanthanides beyond lanthanocenes were used to catalyze the reductive coupling reaction of dienes. La[N(TMS)2h was found to effect the cyclization of 1,5-hexadiene in the presence of PhSiH3 (Eq. 13) [50]. Cyclized products 88 and 89 were isolated in a combined yield of 95% (88 89 = 4 1). It was suggested that the silacycloheptane 89 resulted from competitive alkene hydrosilylation followed by intramolecular hydrosilylation. 

As to the first route, we started in 1969 (1) in investigating unconventional transition metal complexes of the 5 and 4f block elements of periodic table, e.g., actinides and lanthanides as catalysts for the polymerization of dienes (butadiene and isoprene) with an extremely high cis content. Even a small increase of cistacticity in the vicinity of 100% has an important effect on crystallization and consequently on elastomer processability and properties (2). The f-block elements have unique electronic and stereochemical characteristics and give the possibility of a participation of the f-electrons in the metal ligand bond. 

The application of these methods is described in some detail for recovery of base metals and platinum group metals in Sections 9.17.5-9.17.6 focusing mainly on solution-based hydrometal-lurgical operations, largely those involving solvent extraction, because the nature of the metal complexes formed is usually best understood in such systems. NB. Extraction of lanthanides and actinides is not included as this subject is treated separately in Chapters 3.2 and 3.3. 

When not complexed, lanthanide ions have a high affinity for bone in vivo because they act as calcium ion mimics. Because the lanthanides undergo hydrolysis above a pH of 4, they readily form radiocolloids when not complexed, and are then taken up by the liver. This bone and liver uptake results in non-specific radiation doses to non-target (normal) tissues and organs and is undesirable.91 The polyaminocarboxylate class of ligands are considered to be the optimal choice for the basis of BFCAs for the+3 metal cations, including the lanthanides. It is essential that the... 

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