Organometallic Bonding and Reactivity: Fundamental Studies by J.M. Brown, P. Hofmann, P.B. Armentrout, D. Braga, A.

By J.M. Brown, P. Hofmann, P.B. Armentrout, D. Braga, A. Dedieu, P. Gisdakis, A. Görling, F. Grepioni, F. Maseras, N. Rösch, S.B. Trickey

Basic The making and breaking of carbon-metal bonds is key to the entire p- cesses of organometallic chemistry and in addition performs an important position in - mogeneous in addition to heterogeneous catalysis. This fairly blunt assertion - phasises the level to which a formal figuring out of the constitution, energetics and reactivity of C-M bonds is on the middle of the self-discipline. with the intention to settle for it, a formal definition of the phrases concerned is needed. readily we outline the metal-carbon bond in its broadest feel to include carbon associated with transiti- metals, lanthanides and actinides, and major team metals. we don't dist- guish among officially covalent unmarried or a number of bonding at the one hand and q-bonding at the different. within the reports to be defined within the following chapters, the emphasis can be on transition steel complexes and insofar because the enjoyable- mentals come below scrutiny, basic steel alkyls or similar species (metal al- nyl, alkynyl, aryl, or allyl) will play an emphatic half. The primary position of steel alkyls and their congeners and particularly the function in their steel carbon linkage in homogeneous catalysis can be preferred through contemplating a few key response steps resulting in their formation or breakdown. There follows a number of renowned examples of transition steel mediated stoichiometric or catalytic techniques: - In homogeneous hydrogenation of double bonds, the stepwise response of an q2-coordinated alkene with dihydrogen provides first an alkyl steel hydride, after which the decoordinated alkane via removing.

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66 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Topics in Organometallic Chemistry, Vol. M Brown and P. Hofmann © Springer-Verlag Berlin Heidelberg 1999 48 Dario Braga, Fabrizia Grepioni 1 Introduction Traditionally, chemistry has been concerned with atoms and with bonds between atoms and we are all used to teaching students that a chemical reaction is the process in which bonds between atoms are broken and formed on going from reactants to products.

Sievers MR, Armentrout PB (1995) J Phys Chem 99:8135 117. Khan FA, Steele DL, Armentrout PB (1995) J Phys Chem 99:7819 118. Meyer F, Chen YM, Armentrout PB (1995) J Am Chem Soc 117:4071 119. Meyer F, Armentrout PB (1996) Mol Phys 88:187 120. Sievers MR, Jarvis LM, Armentrout PB (1998) J Am Chem Soc 120:1891 121. Meyer F, Khan FA, Armentrout PB (1995) J Am Chem Soc 117:9740 122. Schultz RH, Armentrout PB (1991) J Am Chem Soc 113:729 123. Schultz RH, Armentrout PB (1992) J Phys Chem 96:1662 124. Schultz RH, Armentrout PB (1993) J Phys Chem 97:596 125.

Atomic Displacements . . . . . . . . . Empirical Estimate of Reorientational Barriers . . . . 52 53 53 55 56 3 Organometallic Crystal Isomerization, Phase Transitions and Polymorphism . . . . . . . . . . . . . . . 5 Crystal Polymorphism . . . . . . . Crystals Formed by Structural Isomers . . Pseudo-Polymorphism of Electronic Isomers . Pseudo-Polymorphism Arising from Disorder Crystal Transformations and Dynamics . . . . . 59 60 61 62 62 4 Perspective of an Organometallic Solid State and Materials Chemistry .

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