Advances in Organometallic Chemistry by F. G. A. Stone, Robert West

By F. G. A. Stone, Robert West

Just about all branches of chemistry and fabric technological know-how now interface with organometallic chemistry - the research of compounds containing carbon-metal bonds. This greatly acclaimed serial comprises authoritative experiences that handle all features of organometallic chemistry, a box which has extended vastly because the e-book of quantity 1 in 1964. . presents an authoritative, definitive evaluation addressing all features of organometallic chemistry.. important to all researchers inside this energetic box and is a needs to for each smooth library of chemistry.. top of the range examine publication inside of this speedily constructing box.

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28. 41 Reproduced with permission from the American Chemical Society. 4). ii. Reaction sequence by NMR-monitoring The exact course of the reaction of 1g with 12 (Eq. 41 The reagents (1g and 12) were dissolved at liquid nitrogen temperature in CD2Cl2 and the solution was placed in a pre-cooled (200 K) NMR probe-head. The various NMR spectra were then measured at various temperatures. Equation (22) outlines the resulting reaction sequence. 50 DANIEL KOST AND INNA KALIKHMAN ð22Þ It is quite surprising to find that the monocyclic 13 is not an intermediate on the way to the bis-chelate 61a, but rather the opposite, that 61a forms initially at low temperature as an unstable intermediate.

It follows that the uncommon trans geometry, found in 65 and 66, is the result of steric repulsion between the bulkier Si–Cl and Si–Br bonds and the isopropylidene methyl group. All three dihalo-complexes (the cis-64 and trans-65 and 66) react readily with 56 DANIEL KOST AND INNA KALIKHMAN FIG. 33. 20 Reproduced with permission form Elsevier. TMSOTf, exchanging their halogeno ligands by triflate (Eq. 26), to yield the same trans-ditriflate chelates 67a,b (Fig. 33). ð26Þ The trans geometry is confirmed in solution for 65b–67b by the appearance of a singlet for the methylene protons in the 1H NMR spectra due to C2h symmetry of the trans chelates.

The NOESY spectrum clearly reveals interchange only within each diastereoisomer: 1 ! 1 and 2 ! 2. 47 32 DANIEL KOST AND INNA KALIKHMAN FIG. 17. 47 Reproduced with permission from the American Chemical Society. iv. Correlation between SiCl distance and exchange barrier Support for the assignment of (Ph,Cl) exchange to the lower of the two exchange processes came from an analysis of the X-ray crystallographic data. The activation barriers for this process for the chloro complexes (30c–32c and 35c) in toluene-d8 solutions inversely correlate with the Si–Cl bond lengths in the solid-state (Table XII).

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