Seventh Edition
This edition first published 2019
© 2019 John Wiley & Sons Inc.
Edition History
John Wiley & Sons Inc. (1e, 1988), John Wiley & Sons Inc. (2e, 1994), John Wiley & Sons Inc. (3e, 2000), John Wiley & Sons Inc. (4e, 2005), John Wiley & Sons Inc. (5e, 2009), John Wiley & Sons Inc. (6e, 2014)
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Library of Congress Cataloging‐in‐Publication Data
Names: Crabtree, Robert H., 1948‐ author.
Title: The organometallic chemistry of the transition metals / Robert H. Crabtree (Yale University, New Haven, Connecticut).
Description: Seventh edition. | Hoboken, NJ : Wiley, 2019. | Includes bibliographical references and index.
Identifiers: LCCN 2019003168| ISBN 9781119465881 (hardback) | ISBN 9781119465867 (epub)
Subjects: LCSH: Organometallic chemistry. | Organometallic chemistry–Problems, exercises, etc. | Organotransition metal compounds. | Transition metals.
Classification: LCC QD411.8.T73 C73 2019 | DDC 547/.056–dc23
LC record available at https://lccn.loc.gov/2019003168
Cover Design: Wiley
Cover Image: Courtesy of Robert H. Crabtree
This book is a study of the logic of organometallic chemistry, emphasized in Chapters 1–11, as well as some of its leading applications, emphasized in Chapters 12–16. It should give starting scholars the passport they need to set out on this field, analyze the literature, and develop their own approaches and ideas.
ROBERT H. CRABTREE
New Haven, Connecticut
May 2019
I again thank the many colleagues and readers who kindly helped in some way: Odile Eisenstein, Gary Brudvig, Jim Mayer, Daniel Kim, Jaeyeon Hwang, Michael Jewess, Jeremy Weber, Zican Shen, Hannah Lant, Tom van Westen, and R.K. Sharma. I also thank the Department of Energy, Basic Energy Sciences for funding our work in this area.
Textbooks were apparently highly valued by Dr. Johnson, the very distinguished eighteenth century literary critic, as reported by his biographer and friend, James Boswell:
I [Boswell] ventured to interrogate him [Dr. Johnson], “But, Sir, is it not somewhat singular that you should happen to have Cocker's Arithmetick about you on you[r] journey? What made you buy such a book at Inverness?”—He gave me a very sufficient answer. “Why, Sir, if you are to have one book with you upon a journey, let it be a book of science. When you have read through a book of entertainment, you know it, and it can do no more for you; but a book of science is inexhaustible.”
Journal of a Tour in the Hebrides with Samuel Johnson LL.D. by James Boswell, London, 1785, p. 152.
[ ] | Encloses complex molecules or ions |
□ | Vacant site or labile ligand |
° | Degrees Celsius |
1°, 2°, 3° | Primary, secondary, tertiary. |
A | Associative substitution (Section 4.4) |
acac | Acetylacetonate |
AIBN | Azobisisobutyronitrile (radical initiator) |
AO | Atomic orbital |
Ar | Aryl (e.g. C6H5) |
at. | Pressure in atmospheres |
bipy | 2,2′‐Bipyridyl |
Bu | Butyl |
cata | Catalyst |
Chap. | Chapter |
CIDNP | Chemically induced dynamic nuclear polarization (Section 6.3) |
CN | Coordination number |
cod | 1,5‐Cyclooctadiene |
coe | Cyclooctene |
cot | Cyclooctatetraene |
Cp, Cp* | C5H5, C5Me5 |
Cy | Cyclohexyl |
∂+ | Partial positive charge |
δ | Chemical shift (NMR) |
Δ | Crystal field splitting (Section 1.4) |
ΔEN | Electronegativity difference |
ΔG ‡ ΔH ‡ ΔS ‡ | Free energy, enthalpy and entropy of activation needed to reach the transition state for a reaction. |
D | Dissociative substitution mechanism (Section 4.3) |
D–C | Dewar–Chatt model of M(C=C) bonding involving weak back donation (Section 5.1) |
dσ, dπ | σ‐Acceptor and π‐donor metal orbitals (see Section 1.4) |
diars | Me2AsCH2CH2AsMe2 |
dpe or dppe | Ph2PCH2CH2PPh2 |
dmf | Dimethylformamide |
dmg | Dimethyl glyoximate |
dmpe | Me2PCH2CH2PMe2 |
DMSO | Dimethyl sulfoxide |
d n | Electron configuration (Section 1.4) |
η | Hapticity in ligands with contiguous donor atoms (e.g. C2H4. See Section 2.1) |
E, E+ | Generalized electrophile such as H+ |
e | Electron, as in 18e rule |
e.e. | Enantiomeric excess (Section 9.2) |
en | H2NCH2CH2NH2 |
eq | Equivalent or equatorial |
Et | Ethyl |
EPR | Electron paramagnetic resonance |
Eq. | Equation |
eu | Entropy units |
eV | Electron volt (1 eV = 23 kcal/mol) |
EXAFS | X‐ray absorption edge fine structure spectroscopy |
Fig. | Figure |
Fp | (C5H5)(CO)2Fe |
fac | Facial (stereochemistry) |
GC | gas chromatography |
Hal | Halogen |
HBpz3 | Tris(pyrazolyl)borate |
HMPA | Hexamethyl phosphoramide O=P(NMe2)3 |
HOMO | Highest occupied molecular orbital |
hs | High spin |
I | Nuclear spin |
I | Intermediate substitution mechanism |
IPR | Isotopic perturbation of resonance (Section 10.8) |
IR | Infrared |
κ | Hapticity in ligands with noncontiguous donor atoms (e.g. H2NCH2CH2NH2. See Section 2.1) |
L | Depending on the context, L can be a generalized ligand of any type, or else a 2e ligand in connection with the L model for ligand binding discussed in Section 2.1) |
L n M | Metal fragment with n generalized ligands |
lin | Linear |
lp | lone pair |
ls | low spin |
LUMO | Lowest unoccupied molecular orbital |
μ | Descriptor for bridging with a superscript for the number of metals bridged, as in M3(μ3‐CO) |
m‐ | Meta |
MCP | Metalacyclopropane model of M(C=C) bonding involving strong back donation (Section 5.1) |
Me | Methyl |
mer | Meridional (stereochemistry) |
m r | Reduced mass |
MO | Molecular orbital |
ν | Frequency |
N | Group number of M (=number of valence e in the neutral atom). |
nbd | Norbornadiene |
NHC | N‐heterocyclic carbene (Section 4.2) |
NHE | Normal hydrogen electrode, a common standard potential |
NMR | Nuclear magnetic resonance (Sections 10.2-10.8) |
NOE | Nuclear Overhauser effect (Section 10.7) |
Np | Neopentyl |
Nu, Nu− | Generalized nucleophile, such as H− |
o‐ | Ortho |
OA | Oxidative addition |
OAc | Acetate |
oct | Octahedral (Table 2.6) |
OS | Oxidation state (Section 2.4) |
oz. | Ounce (28.35g) |
p‐ | Para |
PE | Polyethylene |
PP | Polypropylene |
Ph | Phenyl |
pin | Pinacolate |
PNP | A pincer ligand with one nitrogen and two phosphorus donors |
py | Pyridine |
R | Alkyl |
RE | Reductive elimination |
RF | Radiofrequency |
RF | Fluoroalkyl (e.g. CF3) |
Sec. | Section of the book |
SET | Single electron transfer (Section 8.6) |
σ‐CAM | σ‐Complex assisted metathesis |
solv | Solvent |
sq. pl. | Square planar |
sq. py. | Square pyramidal (Table 2.6) |
T | A structure with three of the ligands disposed as in the letter T. |
T 1 | Spin–lattice relaxation time |
tacn | 1,4,7‐Triazacyclononane |
tacn* | N,N′,N″‐trimethyl‐1,4,7‐triazacyclononane |
tbe | t‐BuCH=CH2 |
tet | Tetrahedral |
thf | Tetrahydrofuran ligand (but THF when a solvent) |
triphos | MeC(CH2PPh2)3 |
TBP or trig. bipy | Trigonal bipyramidal (Table 2.6) |
TMEDA | Me2NCH2CH2NMe2 |
TMS | Tetramethylsilyl or tetramethylsilane |
Tp | Tris(pyrazolyl)borate (5.37) |
Ts | p‐TolylSO2 |
TTP | Tricapped trigonal prism (Table 2.6) |
VB | Valence bond |
X | Generalized 1e anionic ligand (Section 2.1) |
Y | A structure with three of the ligands disposed as in the letter Y. |