Progress in Inorganic Chemistry, Volume 22

442 Pages·1977·12.234 MB·English

Progress in
Inorganic Ghernistrg
Volume 22
Advisory Board
THEODORE L. BROWN
UNIVERSITY OF ILLINOIS, URBANA, ILLINOIS
JAMES P. COLLMAN
STANFORD UNIVERSITY, STANFORD, CALIFORNIA
F. ALBERT COTTON
TEXAS A & M UNIVERSITY, COLLEGE STATION, TEXAS
RONALD J. GILLESPIE
McMASTER UNIVERSITY, HAMILTON, ONTALIO, CANADA
GEOFFREY WILKINSON
IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, LONDON,
ENGLAND
PROGRESS IN
INORGANIC CHEMISTRY
Edited by
STEPHEN J. LIPPARD
DEPARTMEOFN CTH EMISTRY
COLUMBUIAN IVERSITY
NEWY ORKN, EWY ORK
VOLUME 22
AN INTERSCIENCEE PUBLICATION
- -
JOHN WILEY & SONS, New York . London Sydney Toronto
An Interscience@P ublication
Copyright 0 1977 by John Wiley & Sons, Inc.
All rights reserved. Published simultaneously in Canada.
No part of this book may be reproduced by any means,
nor transmitted, nor translated into a machine language
without the written permission of the publisher.
Library of Congress Catalog Card Number: 59-13035
ISBN W71-54092-7
Printed in the United States of America
109 8 7 6 543 2 1
Contents
The Coordination and Bioinorganic Chemistry of Molybdenum
BY EDWARDI. STIEFELC,. F. Kettering Research Laboratory,
Yellow Springs, Ohio . . . . . . . . . . . . . . . . . . . . 1
The Derivation and Application of Normalized Spherical Harmonic
Hamiltonians
BY J. C. DONINAI ND B. R. HOLLEBONDEe,p artment of Chemistry,
University of Alberta, Edmonton, Albertu, Canada; and A. B. P.
LEVERD, epartment of Chemistry, York University, Downsview
(Toronto), Ontario, Canada . . . . . . . . . . . . . . . . . 22S
Chemical Applications of Magnetic Anisotropy Studies on Transition
Metal Complexes
BY S. MITRAC, hemical Physics Group, Tata Institute of
Fundamental Research, Bombay, India . . . . . . . . . . . . . 309
Oxidatively Induced Cleavage of Transition Metal-Carbon Bonds
BY G. WILLIADMA UBD, epartment of Chemistry, Stanford
University, Stanford, California . . . . . . . . . . . . . . . ,409
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . .42S
Cumulative Index, Volumes 1-22 . . . . . . . . . . . . . . . .
-435
Progress in
Inorganic Chemistrg
Volume 22
Progvess in Inorganic Chemistry; Volume 22
Edited by Stephen J. Lippard
Copyright © 1977 by John Wiley & Sons, Inc.
The Coordination and Bioinorganic
Chemistry of Molybdenum
.
by EDWARD I STIEFEL
C. F . Kettering Reseurch Laboratory
.
Yellow Springs Ohio
(Contribution No. 539)
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1 . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
A . Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . . 6
B . Previous Reviews . . . . . . . . . . . . . . . . . . . . . . . . . . 7
C . Bioinorganic Aspects . . . . . . . . . . . . . . . . . . . . . . . . 8
I1 . Molybdenum in Biological Systems . . . . . . . . . . . . . . . . . . . . 9
A . Molydbenum Enzymes . . . . . . . . . . . . . . . . . . . . . . . 11
1. Nitrogenase . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2 . Nitrate Keductase . . . . . . . . . . . . . . . . . . . . . . . . 14
3 . Xanthine Oxidase and Xanthine Dehydrogenase . . . . . . . . . . . 1 6
. Aldehyde Oxidase . . . . . . . . . . . . . . . . . . . . . . . . 20
4
5 . SulfiteOxidase . . . . . . . . . . . . . . . . . . . . . . . . . 20
6 . Other Enzymes . . . . . . . . . . . . . . . . . . . . . . . . . 21
B . TheMoCofactor . . . . . . . . . . . . . . . . . . . . . . . . . 21
C . Substrate Half Reactions . . . . . . . . . . . . . . . . . . . . . . 22
111 . The Chemistry of Molybdenum (VI) . . . . . . . . . . . . . . . . . . . 25
A . Structural Studies . . . . . . . . . . . . . . . . . . . . . . . . . 25
1 . Monomeric Coniplexes . . . . . . . . . . . . . . . . . . . . . . 27
2 . Dimeric Complexes . . . . . . . . . . . . . . . . . . . . . . . 29
3 . Peroxo Complexes . . . . . . . . . . . . . . . . . . . . . . . 31
. Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4
B . Molybdates and Thiomolybdates . . . . . . . . . . . . . . . . . . 3 4
C. Halo and Oxohalo Compounds . . . . . . . . . . . . . . . . . . .3 7
D . MoO,L, Complexes . . . . . . . . . . . . . . . . . . . . . . . . 41
E . Reactions and Other Complexes . . . . . . . . . . . . . . . . . . . 43
IV . The Chemistry of Molybdenum (V) . . . . . . . . . . . . . . . . . . .4 5
A . Structural Studies . . . . . . . . . . . . . . . . . . . . . . . . . 46
I . Mononuclear Complexes . . . . . . . . . . . . . . . . . . . . . 47
2 . Dinuclear Complexes . . . . . . . . . . . . . . . . . . . . . .
48
a . Mo,CI,, . . . . . . . . . . . . . . . . . . . . . . . . . .
48
1
.
2 EDWARD I STIEFEL
b . Structures Containing the Linear Mo-0-Mo Bridge . . . . . . . . 4 8
c . Structures Containing the Mo.0. Bridge . . . . . . . . . . . . 50
d . Structures Containing the MoS. Mo Bridge . . . . . . . . . . . 5 3
e. Triply Bridged Structure . . . . . . . . . . . . . . . . . . . . 55
f . Tetrameric Mixed-Valence Structure . . . . . . . . . . . . . . 56
B. Mononuclear Complexes . . . . . . . . . . . . . . . . . . . . . . 57
1 . Monomers Containing the Unit . . . . . . . . . . . . . . 5 7
2 . Nonoxo Mononuclear Mo(V) Complexes . . . . . . . . . . . . . .6 5
C . EPR Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
D . Dinuclear Complexes . . . . . . . . . . . . . . . . . . . . . . . . 74
1 . Complexes Containing the Mo, 0:4 Unit . . . . . . . . . . . . . . 7 4
2. Complexes Containing the Mo, O:Z Unit . . . . . . . . . . . . . . 83
3 . Complexes Containing the p-Sulfido Linkage . . . . . . . . . . . . 87
4 . Other Bridged Structures . . . . . . . . . . . . . . . . . . . . . 90
E . Reactions and Interconversions . . . . . . . . . . . . . . . . . . . . 91
1 . Reactions of Halides and Pseudohalides. . . . . . . . . . . . . . . 91
2 . Interaction of Cysteine and Glutathione with Mo(V) . . . . . . . . . 9 5
a . Cysteine with Mo(V) . . . . . . . . . . . . . . . . . . . . . 95
b . Complex of Mo and Glutathione . . . . . . . . . . . . . . . . 9 9
V. The Chemistry of Molybdenum(1V) . . . . . . . . . . . . . . . . . . .10 0
A . 0x0 Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 102
B . Mo(IV) in Aqueous Solution . . . . . . . . . . . . . . . . . . . . 109
C . Halide and Pseudohalide Complexes . . . . . . . . . . . . . . . . .11 0
D . Eight-Coordinate Complexes . . . . . . . . . . . . . . . . . . . . . 117
E . Cyclopentadienyl Compounds . . . . . . . . . . . . . . . . . . . . 118
F . Unusual Sulfur-Donor Complexes . . . . . . . . . . . . . . . . . .12 0
VI . The Chemistry of Molybdenum(II1). . . . . . . . . . . . . . . . . . . . 121
A . Molybdenum(II1) Trihalides and Related Species . . . . . . . . . . . .12 2
B . Mononuclear Complexes . . . . . . . . . . . . . . . . . . . . . . 125
1 . Structural Studies . . . . . . . . . . . . . . . . . . . . . . . . 126
2 . Preparation and Properties . . . . . . . . . . . . . . . . . . . . 126
3 . Magnetic and EPR Studies . . . . . . . . . . . . . . . . . . . . 131
4 . Electronic Spectral Studies . . . . . . . . . . . . . . . . . . . . 132
5 . The Hexaaquomolybdenum(III) Ion . . . . . . . . . . . . . . . .1 36
C . Dinuclear and Polynuclear Complexes . . . . . . . . . . . . . . . . .13 7
VII . The Chemistry of MoIybdenum(I1) . . . . . . . . . . . . . . . . . . . . 141
A . Monomeric Mo(1l) Complexes . . . . . . . . . . . . . . . . . . . . 142
B . Dimeric Mo(1I) Complexes . . . . . . . . . . . . . . . . . . . . . 146
VIII . Molybdenum Tris(dithio1ene) and Related Compounds . . . . . . . . . . . 1 54
IX. Molybdenum Nitrogen Chemistry . . . . . . . . . . . . . . . . . . . . 160
A . Complexes of Dinitrogen and Their Reactions . . . . . . . . . . . . .16 1
1 . Trans-Mo(N,),(dppe), and Related Species. . . . . . . . . . . . .16 1
a . Synthesis and Structure . . . . . . . . . . . . . . . . . . . . 161
b . Reactions . . . . . . . . . . . . . . . . . . . . . . . . . .
164
(1) Adduct Formation . . . . . . . . . . . . . . . . . . . . 164
(2) Formation of Mo(1) Complexes . . . . . . . . . . . . . .16 4
(3) Ligand Substitution . . . . . . . . . . . . . . . . . . . . 166
COORDINATION AND BIOINORGANIC CHEMISTRY OF Mo 3
(4) Intermolecular Ligand-Exchange Reactions . . . . . . . . .16 7
(5) Reduction of Coordinated Dinitrogen . . . . . . . . . . . .1 68
2. (Ar) Mo(PR.).N. and Related Complexes . . . . . . . . . . . . . .17 1
3 . M'-N=N-Mo Complexes . . . . . . . . . . . . . . . . . .17 3
4 . Molybdocene Derivatives . . . . . . . . . . . . . . . . . . . . . 174
5 . Dinitrogen Reduction in Other Mo Systems . . . . . . . . . . . . .1 76
B . Arylazo and Alkylazo Complexes . . . . . . . . . . . . . . . . . . .1 77
C . Complexes of Hydrazines. Diimines. and Related N Donors . . . . . . .1 80
D . Mo Nitrido Complexes . . . . . . . . . . . . . . . . . . . . . . . 185
E . Nitrosyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 188
1 . Mo(NO),X, Compounds . . . . . . . . . . . . . . . . . . . . 188
2 . Ncutral Complexes of Mo(NO),L,X, and Mo(NO), (LI.) X, . . . . . .1 89
3. Mo(NO)CI, and Dcrivativcs . . . . . . . . . . . . . . . . . . .1 92
4 . Mo(NO),(R,dtc), and MoNO(R,dtc), . . . . . . . . . . . . . . .1 92
5 . Anionic Molybdenum Nitrosyls . . . . . . . . . . . . . . . . . . 1 93
6 . Cationic Molybdenum Nitrosyls . . . . . . . . . . . . . . . . . . 1 93
7. General Considerations and the Catalyzed Olefin Disproportionation
React ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
F . Mo Hydrides and Zerovalent Compounds . . . . . . . . . . . . . . . 1 97
G . Catalyzed Amine Oxidation . . . . . . . . . . . . . . . . . . . . . 198
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
..............
.......A.B.B..R.E.V..IA TIONS
acac- .
acacen-2 I (CH3COCHC(CH3)
2.bis(acetylacetoneimino)ethane
NCH.CH. NCCH3CHCOCHy2)
l-ala I-alanine (CH.CH(NH. )COOH)
ATP adenosine-5'-triphosphate
ADP
adenosine-5'-diphosphate
arphos 1
-diphenylphosphino-2-diphenylarsinoethane
(Ph2PCHZCH2AsPh. )
ha1 2. 3-dimercaptopropanol
bigH biguanide (NH.C(NH)NHC(NH)NH. )
CGHsbigH pheny lbiguani de NH2C(N P1i)N HC( N H)NH2
biPY 2.2 '-bipyridyl (C5H4N)x
4 EDWARD I. STIEFEL
Bu butyl (C4H9)
I-cysteine (NSCH2CHNH2COOH)
CYS
0-Mecys I-cysteine methyl ester (HSCH2CHNH2COOCH3)
CYt cytochrome
dbm- dibenzoylmethide (PhCOCHCOPh-)
diars 1 (ASM~~)~)
,2-bis(dimethylarsino)benzene(C6H4
dien diethylenetriamine (NH2CH2CH2NCH2CHzNH2)
dma N,N-dimethylacetamide ((CH3)2NCOCH3)
dmf N,N-dimethylformamide ((CH3),NCHO)
dmpe ((CH3)2PCH2CH2P-
1,2-bis(dimethylphosphino)ethane
(CH3)2)
dmpm ((CH3)2PCH2P(CH3)2)
bis(dimethy1phosphino)methane
dmso dimethylsulfoxide (CH3SOCH3)
dpae 1,2-bis(diphenyIarsino) ethane (Ph2AsCH2CH2AsPh,)
dpam bis(diphenylarsin0) methane (Ph2AsCHZCH2AsPh2)
dpm- dipivaloylmethide (t-C4HgCOCHCO)-t-C4H;)
dPPe 1,2-bis(diphenylphosphino)ethane (Ph2PCH2CH2PPh2)
dPPm bis(dipheny1phosphino)methane (Ph2PCH2PPh2)
dPPP 1,3-bis(diphenylphosphino)propane
(Ph2PCHZCHZCH2PPh2)
Rzdtc- (RzNCS,)
N,N-dialkyldithiocarbamate
dtd 4,7-dithiadecane (CH3CHZCH2SCH2CH2SCH2CH2CHs)
dth 2,5-dithiahexane (CH3SCH2CH2SCH3)
dtdd 5,8-dithiadodecane (n-C4H@CH2CH2S-n-C4Hg)
Rzdtp- dialkyldithiophosphate ((RO)ZPS:)
edtap4 ethylenediaminetetracetate ((-OOCCHZ)~NCH~CH~N-
(CH2C00-)2)
en ethylenediamine (NHzCHzCH2NH2)
EPR electron paramagnetic resonance
Et ethyl (C2H5)
FAD flavin adenine dinucleotide
d Y glycinc (CH2NH2COOHj
HB(Pz); tris(2-pyrazolyl)hydroborate
hfa hexafluoroacetylacetonate (CF,COCHCOCFy)
his I-histidine ((C3H3N2)CH2CHNH2COOH)
Me methyl (CH3)
mida-2 methyliminodiacetate CH3N(CH2COO-)2
mnt-2 maleonitriledithiolate (1,2-dicyanoethylene-l, 2-dithiolatej
(SzC2(CN, 2>
i-mnt 2 2,2-dicyanoethylene-1 ,1- dithiolate (SZC~(CN),~)
NADH nicotinamide adenine dinucleotide
NADPH nicotinamide adenine dinucleotide phosphate