Clayden 1300 –> to the end of what I’m going to read in the book

For some final thoughts and suggestions for the next edition go to the end of the comments on particular  pages
p.1305 — How are Bu3Sn 0 SnBu3 and LiSnMe3 made?

p. 1312 — Why have the transition elements with s2d1 ( Sc, Y, Lu ) and s2d10 (Zn, Cd, Hg) been left out of the table? Aren’t they used?

p. 1312 — Does Hf from a stable 16 electron complex like Ti Zr Ni Pd and Pt? If not why not.

p. 1312 – Why don’t other metals have a ‘high energy vacant orbita’ allowing adoption of a square planar configuration like Ni, Pd and Pt.

p. 1315 — Remarkably little about the combination of s, p, and d orbitals of the metals and their stereochemistry, and even their size (what are their atomic diameters?). This is a huge shift from everything in the previous 1308 pages. Aren’t these results known? The example of carbon monoxide bond formation is the last time an orbital is shown in this chapter.  Having finished the chapter I probably know why.  The chapter is a densely packed survey of a very large field. Because of the density of information, this chapter is the hardest to read.

p. 1315 — Before plunging ahead to the various types of reactions occuring with transition metals you might list and number the basic types
l. Oxidative Insertion
2. Reductive Elimination
3. Migratory insertion (examples — carbonylation, carbometallation, alkyne insertion)
Having read the rest of the chapter, making such a simple classification explicit before plunging in to the actual chemistry would have improved my comprehesion (and presumably that of others as well).

p. 1315 — Oxidative addition — the term is probably entrenched, but this occurs in the Grignard example given without an external oxidant. Some note should be made of this.

p. 1316 — Reductive elimination — again in the first example given no reducing agent is required, just DMSO and heat. Is this true in general?

p. 1317 — How do we know the structures of the various complexes shown — NMR? Xray crystallography? Chemistry?

p. 1317 — Judging by the distance the two phosphorus atoms must be apart in the right most coordination of Pd in the top row — the coordination sphere of Pd must be large. Calculation: Figure the length of the bond in the aromatic rings as the same as benzene (e.g. 1.39 Angstroms). There are 4 of them between the two Phosphorus atoms — but times cosine of 30 degrees which is .866 — so they are 4 * 1.39 * .866 = 4.8 Angstroms apart. This assumes the Phosphorus atoms are as drawn in the structure given. If not, all bets are off.

p. 1318 — If iron is a good soft nucleophile for alkyl halides with 4 CO’s hanging from it, it must be fairly large. What is its atomic radius. Are the 4 CO’s disposed tetrahedrally at the start of the Sn2 reaction? Also why is an alkyl group a ‘poor ligand’.

p. 1319 — “This is an enormous and rapidly expanding field that could not be discussed without doubling the size of the book !” But what is discussed in the rest of the chapter incredibly powerful. A book of 1160 pages by Hartwig came out in 2010 on just this subject.

p. 1320 — In the first row of equilibria, I don’t see why 2 L appears between16 and 14 electron complexes with palladium.

p. 1324 — What is TBSO — not in the index.

p. 1324 — I think you mean vinyl stannane not vinyl silane ion the second paragraph of the text from the bottom.

p. 1325 — Second paragraph of text. “The choice for R2 is restricted to substitutions with beta-hydrogen atoms: vinyl, allyl . . . “ This would be clearer if you said “The choice for R2 is restricted to substitutions with sp3 hybridized beta-hydrogen atoms: vinyl, allyl . . . “ or “The choice for R2 is restricted to substitutions with eliminatable beta-hydrogen atoms: vinyl, allyl . . . “

p. 1328 — So Boron is a metal ? Well I guess, if aluminum is a metal boron might be. Carbon isn’t a metal (except graphene) but tin certainly is.

p. 1330 — The ene-diyne antibiotics are used by a variety of bacteria to kill each other. Their real interest is the fact that this class of compounds are active against tumors. You really should put in the structure of calicheamicin in the next edition.

p. 1440 –“There are many books devoted entirely to this subject (Organometallic Chemistry) if you wish to take it further.”  Why not mention the ones you like?  Afraid to step on academic toes?

End of Chapter 48:  Organometallic chemistry as described in this chapter seems like a singles bar with a very liberal bartender, allowing anyone present to act in new and uncharacteristic ways.  The chapter is incredibly dense and hopefully will be expanded in the next edition, with some of the less used synthetic approaches mentioned in previous chapters cut.

Now for some final thoughts on Clayden et. al. :

It’s probably the best chemistry textbook I’ve ever seen (for the future chemist).  It would definitely be overwhelming for a premed.  Textbooks are certainly more user friendly than they were 50 years ago.  Here’s the way “Remarks to the Student” begins in my the organic chemistry textbook of 1958 — “It is usually taken for granted that the student who takes up the study of organic chemistry has a thorough knowledge of first-year college chemistry.”  Not exactly warm and fuzzy.

I’m not going to read Chapters 49 – 53.  Why?  Because I’m pretty familiar with this material, particularly the “here’s what NADH looks like” stuff.  I’m sure it’s good, but it’s time for Anslyn and Doughterty now that Clayden has shown me  the lay of the land in Organic Chemistry circa 2000 – 2001.

Putting the book together must have taken an incredible amount of work and the authors deserve our thanks (or at least a beer).  They are currently at work on the next edition (due out Spring 2012) and two major goals of these posts report errors in the first edition and suggestions for improvement.  Clayden has told me that he and his students look at them.

Organic chemistry is just as much  fun as it was 50 years ago, with all sorts of new reactions, rearrangements and clever syntheses to play with and admire.  I don’t see why everyone doesn’t love it.  Oh well . . . .
Here are a few general suggestions for the next edition

#1 Be more quantitative:  Don’t say “A weak bond” — give a number (which is done sporadically throughout the test).  Better, put in a table of bond strengths (realizing that they aren’t always the same e.g. the C – C bond).  A table of atomic diameters (van der Waals radii) would also be good.
#2 When referring back to something in the text , give a specific page number (if possible) rather than a chapter number.  The technology exists for the publisher to do this for you.  Clearly the exact number isn’t known at the time a given chapter is being written.
#3 Put in more detail about the chemistry of Silicon as given in chapter 47 when discussing Silyl enol ethers etc.
#4 Put in a lot more about the orbitals of the transition metal ions in the chapter on organometallic chemistry.
Thanks again, Clayden et. al.
Amen. Selah.
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