Lanthanide and actinide chemistry and spectroscopy: based on a symposium sponsored by the Division of Inorganic Chemistry at the 178th meeting of the American Chemical Society, Washington, D.C., September 10-13, 1979

463 Pages·1980·35.35 MB·English

by  American Chemical Society. Division of Inorganic Chemistry

Lanthanide and Actinide Chemistry
and Spectroscopy
Norman M. Edelstein, EDITOR
org Lawrence Berkeley Laboratory
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2, 19
ber 21/bk- Based on a symposium
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CH80 | of Inorganic Chemistry at
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MU23, the 178th Meeting of the
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by TEblicati September 10-13, 1979.
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131
ACS SYMPOSIUM SERIES
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D.C. 1980
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
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2, 19 Library of Congress CIP Data
ber 21/bk- Lanthanide and actinide chemistry and spectroscopy.
o2 (ACS symposium series; 131 ISSN 0097-6156)
n Oct10.10 Includes bibliographies and index.
N ooi: 1. Rare earth metals—Congresses. 2. Actinide ele­
Ed ments—Congresses. 3. Spectrum analysis—Congresses.
CH80 | I. Edelstein, Norman M., 1936- . II. American
N9 Chemical Society. Division of Inorganic Chemistry. III.
UE3, 1 Series: American Chemical Society. ACS symposium
M2 series; 131.
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NImb QD172.R2L27 546'.41 80-17468
Ue ISBN 0-8412-0568-X ACSMC8 131 1-472 1980
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NISCDate:
Hn
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by TEblicati American Chemical Society
aded Pu aArllt icRleig ihnt st hRise sveorlvuemd.e Tinhdei caaptepse athraen cceo poyfr itghhet coowdnee ra'ts tchoen sbeonttto tmha ot f rethpero gfirrastp hpiacg ec oopfi eesa cohf
nlo the article may be made for personal or internal use or for the personal or internal use of
w specific clients. This consent is given on the condition, however, that the copier pay the
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D stated per copy fee through the Copyright Clearance Center, Inc. for copying beyond that
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The citation of trade names and/or names of manufacturers in this publication is not to be
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permission, to the holder, reader, or any other person or corporation, to manufacture, repro­
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PRINTED IN THE UNITED STATES OF AMERICA
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
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s.or ACS Symposium Series
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9 | http://0131.fw0 M. Joan Comstock, Series Editor
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ber 21/bk- Advisory Board
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n Oct10.10 David L. Allara W. Jeffrey Howe
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CH80 | Kenneth B. Bischoff James D. Idol, Jr.
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MU23, Donald G. Crosby James P. Lodge
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NImb Donald D. Dollberg Leon Petrakis
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NISCDate: Robert E. Feeney F. Sherwood Rowland
CHon Jack Halpern Alan C. Sartorelli
by TEblicati Brian M. Harney Raymond B. Seymour
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In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
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s. FOREWORD
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20080- IN CHEMISTRY SERIES except that in order to save time the
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EN odoi: integrity of the symposia; however, verbatim reproductions of
CH80 | previously published papers are not accepted. Both reviews
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In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
PREFACE
The last published symposium on lanthanide and actinide chemistry,
sponsored by the Division of Inorganic Chemistry and the Divi
sion of Nuclear Chemistry and Technology of the American Chemical
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or Society, was held in 1966. The purpose of this earlier symposium was
s.
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a "to summarize the significant areas of current chemical research. . .
s.
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u1 The same statement may be made about the present symposium; how
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p://pr0 ever, the topics covered differ considerably. For example, there was not
9 | htt0131. one chapter on organolanthanide or organoactinide chemistry in the
ber 22, 2001/bk-1980- ceohaf ratlphieteer r tssry aamnrspeco uosriniuu mtmhi, sew ltehompilieecn .i tnsF tuhhraetvh epe rrl,ee stdeh netot a vtvhoaleiul ameblueilc itiady ag otoifoo dsnilg yon fiff ritcahacent itpo rnaom pooefu rttnhietess
o2 of the elements and their compounds with atomic numbers greater than
n Oct10.10 96. Also, as in other areas of science, new, sophisticated instrumentation
N ooi: is in the process of revolutionizing the quality and type of data obtained
CHE80 | d on the /-block elements and compounds.
N9 This volume is intended to introduce the nonspecialist chemist to
UE3, 1 recent trends in lanthanide and actinide chemistry and spectroscopy, to
M2
V ber summarize this work, and to identify directions for future studies. Inevi
E UNIeptem toaf btlhye, tohreg acnhizaeprte. rs in this collection reflect (to some extent) the tastes
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HNISCn Date: contrIi bwuotiuolnds ,l iDkre. tWo iltlhiaamnk T t. hCea rpnaarltli cfiopra nhtiss hinel pth ien soyrmgapnoisziiunmg thfoer s ptheeci r
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TEcati troscopy part of the symposium, and Drs. John Fackler, Gary Long, and
d by Publi eLfefoorntasr don I nbteehrarlafn toef tohfe tshyem pDoisviuismio na nodf tIhneo rpguabnliicc aCtiohnem oifs trthye foprro tcheeeidr
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oa ings. Acknowledgment is made to the Donors of the Petroleum Research
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w Fund, administered by the American Chemical Society, for partial sup
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D port of this symposium.
Lawrence Berkeley Laboratory NORMAN M. EDELSTEIN
Berkeley, CA 94720
December 21, 1979.
vii
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
1
Nonclassical Activation of Carbon Monoxide by
Organoactinides
TOBIN J. MARKS, JUAN M. MANRIQUEZ, and PAUL J. FAGAN
Department of Chemistry, Northwestern University, Evanston, IL 60201
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or VICTOR W. DAY, CYNTHIA S. DAY, and SARAH H. VOLLMER
s.
ac Department of Chemistry, University of Nebraska, Lincoln, NE 68588
s.
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p://ch0 Abstract
009 | htt0-0131. This article reviews recent results on the carbonylation
28 chemistry of bis(pentamethylcyclopentadienyl) thorium and uranium
ber 22, 1/bk-19 htioynd roocfa rcbayrl boann d mdoinaolxkiydela minitdoe mcoemtapll-ecxaerbs.o n Faancdi lem emtaigl-rnaittorroyg en insbeorn ds
n Octo10.102 icso mopblesxeersv ewd.e re Ini soselavteerda l acnda secsh abriahcatpetoriazceydl abnyd sbiinhgalpe toccarrybsataml oyXl -ray
N ooi: diffraction. The great strength of the metal-oxygen bonding in
CHE80 | d aths esine sthpee crieesa citsi one vicdheenmt isintr ym, ewtrhiiccha l ias ndd escpidecetdrlayl daatlak,o xyasc arwbeenlel ­
N9
MUE23, 1 -idliek e. dialIkny lst, he tchaes e fionfa l thec abrbiso(npyelnattaimone tphryoldcuycctlso paerne taCd-iCen cyol)u pleda ctin
V er cis-1,2-enediolate complexes, while for the corresponding bis(di-
NImb alkylamides), the products are bis(carbamoyl) species. Both
E Uepte types of compound have been characterized by X-ray diffraction.
NISCHDate: S Ttoh em ceacrhbaonni smtioc nodxiisdceu scshieomnsi storyf ocbastealryvteicd hCeOre rmedayu cbtei ono,f ersepleevcainaclely
Hn that involving actinide oxide or actinide oxide supported cata
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TEcati lysts.
d by Publi Introduction
de
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nl Our recent research in actinide organometallic chemistry
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o Q-5) has sought to exploit those features of f-element ions
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which differ from transition metal ions. The goal of our effort
has been to discover and to understand to what degree the large
ionic radii and f valence orbitals might foster a unique new
organometallic chemistry. Exploration has been at both the chem
ical and physicochemical levels with the central issues concerning
the properties of actinide-to-carbon sigma bonds and related
functionalities. We have learned that the thermal stability and
chemical reactivity of these linkages can be modulated to a con
siderable degree (and often in opposite directions) by changes in
the supporting ligands within the actinide ion coordination sphere.
0-8412-0568-X/80/47-131-003$06.25/0
© 1980 American Chemical Society
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
4 LANTHANIDE AND ACTINIDE CHEMISTRY AND SPECTROSCOPY
Thus, while the coordinative saturation of the triscyclopentadienyl
alkyls, alkenyls, alkynyls, and aryls (hydrocarbyls) of thorium
and uranium, M(7]5-CH)R (^J_S_9), affords considerably enhanced
5 5 3 9 9 9
thermal stability over that of the simple homoleptic derivatives
(10,11,12), it is at the expense of chemical reactivity.
In an effort to more finely tune the coordinative saturation
of actinide hydrocarbyls and to provide greater than one metal-
carbon bond for reaction, we have initiated an investigation of
biscyclopentadienyl thorium and uranium chemistry (6,13,14). Sys
tems based upon the pentamethylcyclopentadienyl ligand have proved
to be some of the most interesting and form the basis of this
g article. The advantages of the 775-(CH)C5 ligand are that it
cs.or makes far greater steric demands than 73)55-C5H5 (thus reducing the
a number of large, bulky ligands which can be accommodated at the
s.
ub1 metal center) while imparting far greater solubility and crystal-
9 | http://p0131.ch00 pltehinizsta abldiiilgeiantnyyd.l aCrI(ets pam2)ol—rsHoe abiponpneedrats r;ws i ttthhhi sar te hsatpshe ec ttm heett oh eyfslfc eiCcst(ss ipoo3fn) -htHih nabndo enrcdiysnc gl oof-a
000- common thermal decomposition process, intramolecular hydrogen
28
2, 19 atom abstraction (7_,8,15., 16,17), hence of preserving the metal-
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n Oct10.10 offo rom rgtahen obmaestiasl lfico r caonm peoluanbdosr.a te and extremely reactive new class
N ooi: The purpose of this article is to review the chemical,
CHE80 | d physicochemical, and structural properties of bis(pentamethyl
N9 cyclopentadienyl) actinide compounds with respect to one reagent:
UE3, 1 carbon monoxide. The interaction of organometallic complexes with
M2
V er carbon monoxide is a subject of enormous technological importance.
NImb Vast quantities of acetic acid, alcohols, esters, and other im
E Uepte portant chemicals are presently produced using organic feedstocks,
HS carbon monoxide, and homogeneous catalysts of the Group VIII
NISCDate: utnrdaenrssittoioodn mfertoaml sm od(e18l, 1s9t,u2d0i)e.s anMdu chis obfa stehdi s upcohne mithset ry,f cliass nsoiwc alwM ell-
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TEcati carbon sigma bond to form an acyl derivative (A) (equation (l))
d by Publi (21,22,23). An industrially important example of this type of
de chemistry is the rhodium catalyzed hydroformylation cycle illus*
a
o trated in Figure 1 (18). It is not clear, however, that the
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M + CO^dMf-CO f=^M-C=0 (l)
A
classic picture of CO activation established for low-valent,
"soft11, mononuclear, Group VIII metal complexes is complete or
accurate in describing the mechanisms of Fischer-Tropsch (24-28),
methanation (24-28), ethylene glycol synthesis (29), and other
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
1. MARKS ET AL. Nonclassical Activation of Carbon Monoxide 5
reactions in which drastic changes in the CO molecule such as
facile deoxygenation and homologation are occurring. Clearly
there is a necessity to develop new carbon monoxide chemistry and
to elucidate new reaction patterns. Such research is essential to
understanding the fundamental aspects of processes which will be
of ever-increasing importance in an economy shifting to coal-based
feedstocks. It will be seen that the carbonylation reactions of
bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and related
compounds differ dramatically from the "classical" pattern and af
ford a better insight into the reactivity of carbon monoxide at
metal centers which exhibit both high oxygen affinity and high
g coordinative unsaturation. In the sections which follow we con
or
s. sider first the chemical and then the structural aspects of this
c
s.a problem.
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9 | htt0131. The sequence shown in equations (2) and (3) offers an effec
20080- tive route to monomeric, highly crystalline, thermally stable
2, 19 thorium and uranium organometallies with either one or two metal-
ber 21/bk-
o2 2(CH)C- + MC1 t0^gg>M[(CH)C1Cl + 2Cl" (2)
n Oct10.10 3 5 5 4 3 5 5 2 2
N ooi: M = Th,U
CHE80 | d
UEN3, 19 M[(CH3)5C5]2C12 + 2RLi etggj °r> M[(CH3)5C512R2 4- 2L1C1 (3)
M2
V er M « Th, R * CH, CHSi(CH), CHC(CH), CHCH, CH
NImb M « U, R * CH,3 CHS2i(CH)3,3 CHC2 H 3 3 2 6 5 6 5
E Uepte 3 2 3 3 2 6 5
NISCHDate: S csuabrsbeoqn uesnitg mar ebaocntdiso n(s6 w,e30r,e3 1t.h)o .r ouAglhll yc ocmhpaournadcst esrhiozwend biyn etlheesmee ntaanld
Hn analysis, cryoscopic molecular weight in benzene (solubility per
Co
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B C
M = U M = Th,U
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
6 LANTHANIDE AND ACTINIDE CHEMISTRY AND SPECTROSCOPY
The reaction of Th[(CH)C](CH) and U[(CH)C](CH)
3 5 5 2 3 2 3 5 5 2 3 2
with carbon monoxide is quite rapid (6,32,33.) • At -80°C in tolu
ene solution, these compounds absorb 2.0 equivalents of carbon
monoxide fet less than one atmosphere pressure) within 1 hour.
Upon warming to room temperature, the dimeric products (l) are
isolated in essentially quantitative yield (equation (4);. The
infrared spectra (Vg-Q - 1655 cm"1; i/_ = 1252, 1220 cm"1) as
c0
well as the single methyl resonance in the1 H NMR spectrum strong
ly suggests that C-C coupling of the inserted carbon monoxide
2M[(CH)C](CH) + 4C0 t0lU^6 >fM[ (CH)C] (0C(CH)= C(CH^O^
org 3 5 5 2 3 2 -80 3 5 5 2 3 (4)
s.
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s.a la M = Th (colorless crystals)
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28
2, 19 CH CH
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N on Octooi: 10.102 -o' D vo-
CHE80 | d fraction studies on ^a. (6,32,33). As can be seen in Figure 2,
N9 four carbon monoxide molecules have been coupled to form four
UE3, 1 thorium-oxygen bonds and, stereospecifically, two cis-substituted
M2
NIV mber mcoanr bo"nb-ecnta rbsoann ddwoiucbhl"e cboonnfdisg.u raTtwioo n T(h3[4()C Ha3)r5eC5 ]c2 omupnointes ntisn tohfe a c otme n-
E Uepte atom metallocycle. The enediolate ligands are essentially planar
HS with genuine C-C double bonds (Ci-C = C,-C' = 1.33(2)A). Fur
HNISCn Date: ther Asst ruac tpurreallu dree tmoa rdkiss caursesi rneg seardvdeidt2 ifoonra l1t hfe-2 efloelmleonwti ncg hesmeicsttiroyn,. it
TECcatio pise raitm etnhtiss wpiotihn tt hwoer btihs cnyoctlionpge ntthaed ireensyullst s ofo fe acralryb otnryalnasttiioonn emxe tals.
d by Publi As is the case for the actinides, these elements in the higher
de oxidation states exhibit a great affinity for oxygen-donating lig
a
o ands (35,36), and their chemistry will place further actinide re
nl
w sults in a more meaningful perspective. Floriani and coworkers
o
D have carried out an extensive investigation of the reaction of
biscyclopentadienyl titanium, zirconium, and hafnium bishydro-
carbyls and halohydrocarbyls with carbon monoxide (equations(5)
and (6)) (37.>38^39_). Only monocarbonylation is observed. Similar
M(CH)R + CO ^=± M(CH)(C0R)R (5)
5 5 2 2 5 5 2
M = Zr, Hf
R = CH, CHCH, (CH not reversible)
3 2 6 5 6 5
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.
MARKS ET AL. Nonclassical Activation of Carbon Monoxide
HRh(CO)L
3
/
L=<£P
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CHCH0 ^H R^C0 ) L^
3 7
HRh(CO)L ,
2
CHC-Rh(C0)L HC — CHCH
s.org 3 57 0II *\ 2 2 J 3
c
s.a C3H7Rh(C0)2l-2 C3H7Rh(CO)L2
ub1 4
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20080- Figure 1. A proposed mechanism for the rhodium-catalyzed hydr of or my lotion
2, 19 of propylene (IS)
ber 21/bk-
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n Oct10.10
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CHE80 | d
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Journal of the American Chemical Society
Figure 2. ORTEP drawing of the nonhydrogen atoms for the [Th(7f-(CH)-
35
C)2(p-02C(CHs)2)]2 molecule, la. All atoms are represented by thermal vibra
5 2
tional ellipsoids drawn to encompass 50% of the electron density. Atoms of a
given type labelled with a prime (') are related to those labelled without by the
crystallographic inversion center midway between the two thorium atoms. The
crystallographically independent pentamethylcyclopentadienyl ligands are la
belled A and B, respectively (32).
In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1980.