Progress in inorganic chemistry. Volume 58

525 Pages·2014·14.958 MB·English

by  Karlin, Kenneth D.

Progress in
Inorganic Chemistry
Volume 58
Advisory Board
JACQUELINEK.BARTON
CALIFORNIAINSTITUTEOFTECHNOLOGY,PASADENA,CALIFORNIA
SHUNICHIFUKUZUMI
OSAKAUNIVERSITY,OSAKA,JAPAN
CLARKR.LANDIS
UNIVERSITYOFWISCONSIN,MADISON,WISCONSIN
NATHANS.LEWIS
CALIFORNIAINSTITUTEOFTECHNOLOGY,PASADENA,CALIFORNIA
STEPHENJ.LIPPARD
MASSACHUSETTSINSTITUTEOFTECHNOLOGY,CAMBRIDGE,
MASSACHUSETTS
JEFFREYR.LONG
UNIVERSITYOFCALIFORNIA,BERKELEY,CALIFORNIA
THOMASE.MALLOUK
PENNSYLVANIASTATEUNIVERSITY,UNIVERSITYPARK,PENNSYLVANIA
TOBINJ.MARKS
NORTHWESTERNUNIVERSITY,EVANSTON,ILLINOIS
JAMESM.MAYER
UNIVERSITYOFWASHINGTON,SEATTLE,WASHINGTON
DAVIDMILSTEIN
WEIZMANNINSTITUTEOFSCIENCE,REHOVOT,ISRAEL
WONWOONAM
EWHAWOMANSUNIVERSITY,SEOUL,KOREA
VIVIANW.W.YAM
UNIVERSITYOFHONGKONG,HONGKONG
PROGRESS IN
INORGANIC CHEMISTRY
Editedby
KennethD.Karlin
DEPARTMENTOFCHEMISTRY
JOHNSHOPKINSUNIVERSITY
BALTIMORE,MARYLAND
VOLUME 58
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LibraryofCongressCatalogNumber:59-13035
ISBN978-1-118-79282-7
PrintedintheUnitedStatesofAmerica
10 9 8 7 6 5 4 3 2 1
Contents
Chapter1 Tris(dithiolene)Chemistry:AGoldenJubilee ............... 1
STEPHENSPROULES
Chapter2 HowtoFindanHNONeedleina(Bio)-ChemicalHaystack .. 145
FABIODOCTOROVICH,DAMIANE.BIKIEL,JUANPELLEGRINO,
SEBASTIÁNA.SUÁREZ,andMARCELOA.MARTÍ
Chapter3 PhotoactiveMetalNitrosylandCarbonylComplexes
DerivedfromDesignedAuxiliaryLigands:AnEmerging
ClassofPhotochemotherapeutics ....................... 185
BRANDONJ.HEILMAN,MARGARITAA.GONZALEZ,and
PRADIPK.MASCHARAK
Chapter4 Metal–MetalBond-ContainingComplexesasCatalystsfor
C-HFunctionalization ............................... 225
KATHERINEP.KORNECKI,JOHNF.BERRY,
DAVIDC.POWERS,andTOBIASRITTER
Chapter5 ActivationofSmallMoleculesbyMolecular
UraniumComplexes ................................. 303
HENRYS.LAPIERREandKARSTENMEYER
Chapter6 ReactiveTransitionMetalNitrideComplexes ............. 417
JEREMYM.SMITH
SubjectIndex ................................................. 471
CumulativeIndex.............................................. 495
v

Tris(dithiolene) Chemistry: A Golden Jubilee
STEPHENSPROULES
WestCHEM,SchoolofChemistry,UniversityofGlasgow,Glasgow,
G128QQ,UnitedKingdom
CONTENTS
I. INTRODUCTION
II. LIGANDS
A. AreneDithiolates
B. AlkeneDithiolates
1. Sulfur
2. CarbonDisulfide
3. PhosphorusPentasulfide
4. OtherSulfurSources
C. Dithiones
III. COMPLEXES
A. Metathesis
B. Redox
C. Transmetalation
IV. STRUCTURES
A. Beginnings
1. NeutralComplexes
2. ReducedComplexes
3. IsoelectronicSeries
B. Redux
1. TrigonalTwist
2. DithioleneFold
3. OxidizedLigands
ProgressinInorganicChemistry,Volume58,FirstEdition.EditedbyKennethD.Karlin.
2014JohnWiley&Sons,Inc.Published2014byJohnWiley&Sons,Inc.
1
2 STEPHENSPROULES
V. THEORY
A. Hückel
B. Fenske–Hall
VI. ELECTROCHEMISTRY
VII. MAGNETOMETRY
VIII. SPECTROSCOPY
A. Vibrational
B. Electronic
C. NuclearMagneticResonance
D. ElectronParamagneticResonance
1. SpinDoublet
2. SpinQuartet
E. X-RayAbsorptionSpectroscopy
1. MetalEdges
2. SulfurK-Edge
F. Mössbauer
IX. SUMMARY
A. Group4(IVB)
B. Group5(VB)
C. Group6(VIB)
D. Group7(VIIB)
E. Group8(VIIIB)
F. Group9(VIIIB)andBeyond
X. CONCLUSIONS
ACKNOWLEDGMENTS
ABBREVIATIONS
REFERENCES
I. INTRODUCTION
The search for organometallic compounds with sulfur-donor ligands gave
inorganicchemistryitsfirsttris(dithiolene)coordinationcompoundin1963(1).
Anticipating a combination of CO and sulfur-donor ligands, King (1) apatheti-
cally described the product of the reaction of bis(trifluoromethyl)dithiete with
molybdenum hexacarbonyl as a hexavalent metal coordinated to three as yet
unidentified dithiols. The first bis(dithiolene) homologues with late transition