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Inorganic Syntheses. Volume 33 - Coucouvanis D.

Coucouvanis D. Inorganic Syntheses. Volume 33 - University of Michigan, 2002. - 299 p.
Download (direct link): inorganiksintesis2002.djvu
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trifluoromethanesulfonate {/flc-[Re(CO)3(bpy)(py )](CF3S03)}
228
39. RSi(OH)3 and RSi(NH2)3 [R = 2,6-iPr2C6H3N(SiMe3)]: Synthesis
of Stable Organosilanes with Three Functional Groups .............
230
A. [2,6-:Pr2C6H3N(SiMe3)]Si(OH)3.................................
231
B. [2,6-:Pr2C6H3N(SiMe3)]Si(NH2)3 ...............................
232
40. Fluorination with Me3SnF: Synthesis of Cyclopentadienyl-Substituted
Group 4 Metal Fluoride Complexes..................................
234
A. Pentamethylcyclopentadienyl(titanium trifluoride)
[(7j5-C5Me5)TiF3]............................................
234
B. PentamethyIcyclopentadienyl(zirconium trifluoride)
{[(7j5-C5Me5)ZrF3]4} ........................................
235
C. Pentamethylcyclopentadienyl(hafnium trifluoride)
{[(775-C5Me5)HtF3]4} ........................................
236
D. Pentamethy Icy clopentadienyl(titanium oxo fluoride)
{[(775-C5Me5)TiFO]4} ........................................
236
E. Pentamethylcyclopentadienyl(titanium imidophenyl fluoride)
{[(775-C5H4Me)TiF(NPh)]2} ...................................
237
XXIV
Contents
F. Bispentamethylcyclopentadienyl(tltanimn fluoride)
(775-
C5Me5)2TiF................................................. 238
41. Seven-Coordinate [2()3()2], [M2(CO )3(NCMe)(PPh3)],
and Alkyne [MI2(CO) (NCMe) (?/2-RC2R)2] Complexes of Molybdenum(lI)
and Tungsten(H) ...................................... 239
A. Diiodo(tricarbonyl)bis(acetonitrile)molybdenum(n)/
tungsten(TI)
................................................... 240
B. Diiodo(carbonyl)(acetonitrile)bis(diphenylacetylene)
[tungsten(TI)]
................................................. 241
C. Diiodotricarbonyl(acetonitrile)triphenylphosphine
[tungsten(TI)]
................................................. 242
42. Chlorothiocarbonyl-bis(triphenylphosphine)iridium(I)
[IrCl(CS)CPPh3)2]
................................................... 244
Contributor
Index.......................................................... 247
Subject Index
............................................................. 249
Formula Index
............................................................. 255
INORGANIC SYNTHESES
Volume 33

Inorganic Syntheses, Volume 33. Edited by Dimitri Coucouvaiiis Copyright
(c) 2002 John Wiley & Sons, Inc. ISBNs: 0-471-20825-6 (Hardback); 0-471-
22450-2 (Electronic)
Chapter One
SYNTHESES OF SELECTED SUPRAMOLECULES
1. TOWARD MAGNETIC BUILDING BLOCKS: SYNTHESIS OF A PLANAR Co(III)-CATION
RADICAL-COBALT(III) COMPLEX OF THE BINUCLEATING LIGAND 1,2,4,5-
TETRAKIS(2-H YDROX Y-2-METHYLPROPANAMIDO)BENZENE
Submitted by SCOTT W. GORDON-WYLIE,* WYNDHAM B. BLANTON,* BRIAN L.
CLAUS,* COLIN P. HORWITZ,* and TERRENCE J. COLLINS* Checked by COLETTE
BOSKOVIC and GEORGE CHRISTOU1
The design of supramolecular architectures has focused on the synthesis
of small subunits that bind to each other in a predictable fashion to
form extended solids. How such molecular building blocks may be
constructed has been discussed in detail.1-9 In the design of molecular
magnetic structures, the key factors necessary to promote magnetic
exchange couplings of a particular type between two or more spin carriers
have also been stated eloquently.10-15 Despite significant advances in
the general research area, there remains a dearth of magnetic building
blocks suitable for the construction of extended, well-ordered, magnetic
solids. Herein is reported the synthesis of a potentially useful magnetic
building block, the () complex16 of the multinucleating ligand
1,2,4,5-tetrakis(2-hydroxy-2-methylpropanamido)benzene [H(k4 :k4-/--
)].
* Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA
15213.
* Indiana University, Bloomington, Indiana 47405-4001.
1
2 Syntheses of Selected Supramolecules
Five features of the Co??1 (k4:k4-^HMPA-B) system considered to be
important for the preparation of a supramolecular magnetic solid are as
follows:
1. Bimetallic complexes with planar four-coordinate ions in the
primary diamido-iV-dialkoxido sites are capable of achieving planarity
across the primary metal, the ligand donor atoms, and the central
aromatic ring. This planarity is useful for reducing the complexity of
derivative network solids.
2. The ligand strongly coordinates two primary metal ions, each in a
strong -donor environment, stabilizing the intermediate spin, 5=1,
() state.
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