Chemistry and catalysis advances in organometallic chemistry and catalysis
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715 single-pot synthesis, 15, 22–23 skeletal rearrangements, 207–221 small molecules, functionalization (see alkane functionalization) S M
solar energy, 519, 520, 525 solar light simulator, 508 soluble guanylate cyclase (sGC), 547, 553 solvent-free peroxidative oxidations, 234, 237, 239 Sonogashira coupling, 152 spectroelectrochemistry, 673 square planar complexes, 506, 681 stealth nanoparticles, 574 structure-reactivity relationship, 653 structure-redox properties relationships (see redox potential-structure relationships) styrene, 65 subcutaneous glioma, 574 sulfides,
oxidation, with Mo catalysts, 306–307 sulfones, formation, with Mo catalysts, 306 sulfoxides, formation, with Mo catalysts, 305–306 reduction, with Mo catalysts, 308 oxidation, with Mo catalysts, 306 sumanene complex, 473–482 supported catalysts, metal composite, 240, 242 polystyrene supported, 227–231, 289 preparation, 228–229 sustainable energy, 494, 501 Suzuki-Miyaura coupling, 149 syngas conversion, 3 synthetic photochemical processes, 520 tamoxifen, 566, 567, 569, 633–635 target proteins, 576 targeted chemotherapy, 605, 606 target-specific complexes, 593–599 tautomers, 194–195 TBHP (tert -butylhydroperoxide), O–H activation (see bond activation) sulfides and sulfoxides oxidation, catalysed by Mo complexes 306–308 alcohols oxidation 234, 236–238 technetium 549, 589–602 template synthesis, 117 TEMPO radical, 233, 608–611 tetracarbene complex, 117, 122 tetrahydrofolate, 523 tetralin, 61 theragnostics, 619, 626 thermal decomposition, 451, 454 thermodynamic potentials, 524 thiazoline based ligands, 185–194 thioether, 668–671, 673 thioorganics, 295–296, 299 three-component reaction, 84, 92–93, 203 toluene, 62 topoisomerases, 606 transfer hydrogenation, 3 transition metal hydrides, acidity, 101 basicity, 105 proton accepting ability, 101 proton donor, 105, 107 transition state, 43, 49 transportable energy, 518 tricarbonyl complexes, 589, 592, 593, 595, 597–602 trifluoroacetic acid (TFA), 21–23, 102 trinuclear assembly, 411, 413, 417 trinuclear triangular Cu(II), 409–416 triosmium dodecacarbonyl, 8 tris(pyrazolyl)borate, 15 tris(pyrazolyl)methanes, 15, 286–293 tris(pyrazolyl)methane sulfonate, 15, 289 turnover number (TON), 5, 8, 11, 17, 18, 21, 32, 236–239, 286, 288–292 tyrosine derivatives, 227–230 tyrosine kinases, 606, 607 unsaturated substrates, 81, 93, 172–181 valence electron, 669, 674 vanadium catalysts (see metal catalysts and complexes) alkane carboxylation, 17–22 alkane oxidation, 12, 17–22, 286, 287, 289–291 sulfoxidations, 227, 230–231 vinylidene, 682, 683, 685 vitamin B12, 563 water gas shift reaction, 3, 550, 554 water soluble complexes, 15, 17–25, 27, 28, 30, 35, 199–204, 549, 557
wavelength, 486 WAXS (Wide Angle X-ray Scattering) analysis, 427 wind tower, 518, 519 working carbon, 513, 517 zirconium, 89–94, 316–321 Zeise’s salt, xi Figure 1 ICOMC Silver/Gold Jubilee medal. RH Mo(CO)
6 + O
2 { Mo VI =O}
h ν { Mo V =O} { Mo V −OH } R O 2 R OO R OO H Figure 1.5 Mechanism proposed for the photooxygenation of alkanes, RH, in the presence of Mo or W carbonyls. Advances in Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book, First Edition. Edited by Armando J. L. Pombeiro. © 2014 John Wiley & Sons, Inc. Published 2014 by John Wiley & Sons, Inc.
{V} N O O O N O OH H O H H {V} = V(O 2 ) {V} N O O O N O HO H {V} N O H O O N O HO {V} N O O O N O HO
O O
[V]' O H (a) (b)
(c) [V] = V(O
2 )(HO)(H
2 O)
2 )(H
2 O) 2 H {V} = V(O 2 ) Scheme 2.6 Examples of transition states (TSs) involved in a proton-transfer step from a ligated H 2 O
to an oxo ligand on the way to generate the hydroxyl radical: (a) six-membered TS (water-assisted H + -transfer) at a PCA-V catalyst (PCA =pyrazine carboxylate) [40]; (b) five- or four-membered TSs (PCA-assisted H + -transfer, “robot’s arm” mechanism) at a PCA-V catalyst [43–45]; and (c) six-membered oxo-divanadium TS at a divanadate-type model [42]. C
1/2 S 2
8 2 − SO 4 − • HSO
4 −
R • • 1 2 S 2 O 8 2 − SO 4 − •
C (
)OSO 3 − R CO OH H 2 O H SO 4 −
4 M
M
−1 + 5 5' 6 2H 2 O H 3 O +
C (
)OSO 3 H HSO 4 − −SO 4 2 − SO 3 7a 7 8 O
R CO
Main radical mechanism of the hydrocarboxylation of alkanes with peroxydisulfate, CO, and water, in aqueous (H 2 O/MeCN) medium [53]. The minor 7 (or 7a) to 8 alternative pathway does not concern water as the hydroxylating agent. RH R • S 2 O 8 2 −
CO OH
3 COOH
( RH ) CF 3 COO
• (
• )
R C [V V ](O)
[V IV ]{OO C ( O ) R } [V V ](OO)
(HS 2 O 7 − ) H 2 SO 4 H 2 SO 5 (HS 2 O 8 − )
CO O
(b) RH +
CO R CO OH Cat. K 2 S 2 O 8 / TFA , 80 °C (a)
(H 2 SO 4 ) HSO 4 SO 4 −(HSO 4 ) CO Δ
Alkane carboxylation with CO and K 2 S 2 O 8 , in TFA: (a) General reaction [13, 17, 54–62] and (b) proposed mechanism for an oxo-vanadium catalyst [54, 55]. Figure 3.1 X-ray crystal structures of complexes [Cu 2 (μ−Hbdea) 2 (N 3 ) 2 ] (3), [Cu 3 (μ−H
2 tea
) 2 (μ−poba) 2 H 2 O] · 4H
2 O (4), and [Cu 3 (
3 - BO)( μ-H 3 bts) 3 ][BF
4 ]2H
2 O (5). All H atoms, [BF 4 ]
anion (in 5), and crystallization H 2 O molecules (in 4, 5) are omitted for clarity. Color codes: Cu, green balls; O, red; N, blue; C, cyan; B, dark green ball. Adapted from References 6, 11, and 13. Figure 3.2 X-ray crystal structures of complexes [Cu 4 (μ
− O)(μ 3 −tea) 4 (μ 3 −BOH) 4 ] [BF 4 ] 2 (6) [Li (H 2 O ) 4 ][Cu 4 μ−Hbes) 4 (μ−ba)] · H 2
4 ] − anions (in 6), [Li (H 2 O ) 4 ] + cations, and crystallization H 2 O molecules (in 7) are omitted for clarity. Color codes: Cu, green balls; O, red; N, blue; C, cyan; B, dark green balls. Adapted from References 6 and 14.
Figure 3.3 X-ray crystal structures of 1D and 2D polymers [Cu 2 (
2 tea)
2 ( μ 2 −tpa)]
n ¨ı2nH
2 O (8) and [Cu 2 (
3 −H 2 tea) 2 (μ 4 −pma)
{Na 2 (H 2 O 4 } n 10 nH 2 O (9), respectively. All H atoms and crystallization H 2 O molecules are omitted for clarity. Color codes: Cu, green balls; O, red; N, blue; C, cyan; Na, magenta. Adapted from References 6 and 8. (a)
(b) Figure 4.6 X-ray structures of (a) (PCP−CH 2
2 − O
2 CMe
) and (b) cyclometalated (PCP)Ir(acetate), [κ 4 −C 6 H 3 −2− (CH
2 P t Bu 2 )−6 − (CH 2 P t Bu (CMe
2 CH 2 ))]Ir(κ 2 −O 2 CMe
). (a) (b)
Figure 5.1 General structure of the Keggin-type (a) and sandwich-type (b) transition metal substituted polyoxometalates (TMSPs) used in catalysis; W (green); O (red); heteroatom X (yellow); transition metal M (pink). 3.5
3.0 2.5
ppm 6.70
6.75 6.80
6.85 6.90
6.95 7.00
7.05 7.10
7.15 7.20
7.25 7.30
7.35 7.40
ppm 4.5
4.4 4.3
4.2 4.1
4.0 3.9
3.8 3.7
ppm 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 ppm (a)
(b) Figure 6.1 1 H– 1 H NOESY (a) and 1 H–
C HSQC (b) spectra of [8-I-8 -(2,5-Me 2 C 6 H 3 )-3,3 -Co(1,2-C 2 B 9 H 10 ) 2 ] − .
(a) (b)
Figure 6.2 Molecular structures of [8-I-8 -Ph-3,3 -Co(1,2- 2 B
H 10 ) 2 ] − (a) and [8-I-8 -(2,5-Me 2 C 6 H 3 )-3,3 -Co(1,2-C 2 B 9 H 10 ) 2 ] − (b)
anions. Adapted with permission from Reference 21. Copyright (2010) American Chemical Society. Ni PPh 3 PPh
3 Ni Ph H H Ni Ph H H PPh 3 Ph 3 P H H Ph Ph Ph H Ph β β' C C' "Heck-type" "ene-reaction-type"
elimination β'-H / reductive elimination Scheme 7.3 Proposed mechanism for reaction of Ni–carboryne with alkenes. 0.006 0.026 0.010
0.037 (a)
(b) Figure 8.3 (a) Optimized structure of dihydrogen-bonded adduct between ( tBu PCP)Ni(H) and CpWH(CO) 3 with selected bond lengths ( ˚ A). Hydrogen atoms of the tBu PCP ligand are omitted for clarity. (b) Fragment of molecular graph of the system. Electron density at the (3,–1) bond critical point and bond order (as a delocalization index [21], in bold italic) are reported for W–H · · · H–Ni and C–H · · · H–Ni contacts. Color codes: •-bond critical points, •-ring critical points. 0.0 −27.4
−19.7 −11.2
−21.6 −4.7
−2.7 Figure 8.6 Optimized (DFT M05) geometries and energy profile ( E, kcal/mol) calculated for protonation of Cp ∗ MoH(CO)(PMe 3 ) 2 by CF 3 COOH (one and two molecules) in gas phase. Selected bond lengths are reported ( ˚ A). Hydrogen atoms of CH 3 groups are removed for transparency. Data from Reference 43. (a) (b)
Figure 12.6 The molecular structures of 4-2; (a) Z = CO 2
Z = COMe. Route I
Route III [M]
N C R 1 C N R 3 R 2 R 4 O O N C R 2 N N N Route IV Route V
[M] C N R 1 C N R 3 R 2 R 4 O Route II [M] N C N O C R 2 R 1 [M]
N C N O C R 3 R 1 R 2 R 4 N N N [M]
N N N C N R 1 [M]
C N N N N
Metal-bound isocyanide R 1 [M] C O N C N R 1 R 2 R 4 R 3
Metal-mediated dipolar cycloaddition to nitriles and isocyanides and dipoles employed.
N O PPh 2 PPh
2 N O Ph 2 P PPh 2 N O PPh
2 PPh
2 N O Ph 2 P PPh 2 H H Tautomeric / Isomeric Forms CH 2
2 Stable as free ligands Stabilization by metal coordination required Scheme 14.27 [Au]
Nu [Au]
Nu [Au]
Nu 1 2 3 H H H − H [Au] Nu [Au] Nu [Au]
Nu + H − [Au] H Nu H Nu H Nu Protodeauration sequence Hydrofunctionalized products
NuH = H 2 O [Au] H 2 O H OH H OH H O H Scheme 16.5 [Au] Nu [Au] Nu E [Au] Nu β [Au] Nu [Au]
Nu β E E Electrophilic trapping
[Au]
Nu [Au]
Nu E E Carbene reactivity Carbocationic reactivity Products Products
6 ′ 7 ′ Carbene
mesomeric form Carbocationic mesomeric form [Eq 1]
[Eq 2] [Au]
Nu [Au]
Nu LG LG − LG [Au] Nu [Au]
Nu [Eq 3]
8 8 ′ Scheme 16.6 M L L S R ′ Pd R 2 B X M S OH L R ′ R 1 L OH L L Thiophilic Borophilic Pd B
R 2 OH R 1 L HO L Kinetic activation Thermodynamic bookkeeping Figure 23.2 Dual thiophilic–borophilic activation of transmetalation. R 1 S R ′ R 2 B (OH) 2 +
+ R 1 R 2 + R ′ S Cu Cu - OCOR ′′ + R ′′CO 2 B (OH) 2 Pd cat O O OH Cu O O HO Cu Me Me O O Cu O O Cu S S CuTC Cu(I) thiophene-2-carboxylate CuMeSal Cu(I) 3-methylsalicylate Pd R 2 B OCOR
′′ Cu S OH L R ′ R 1 L OH L L Thiophilic borophilic
cofactor enhanced kinetics and thermodynamics
Pd-catalyzed, Cu(I) carboxylate-mediated desulfitative catalysis. 2.430 1.677
2.666 1.666
1.691 1.182
2.330 2.182
1.478 1.812
1.725 1.386
1.427 L M N L ′ TS L ′M TS MN 2.362 0.983 1.773
1.800 2.080
1.429 1.562
2.077 2.081
1.737 0.989
1.822 2.108 1.423 1.399 1.317
1.662 1.750
0.984 1.808
2.111 1.769
1.888 1.309
1.542 2.385
1.799 2.210
1.538 1.797
Figure 24.9 Intermediates and transition states in the sulfoxide reduction catalyzed by MoO 2 Cl
(H 2 O) 2 (L) with relevant distances ( ˚ A).
AcO R 3 + O R 2 R 1 O R 2 R 1 R 3 Pd(Ph
3 ) 4 10 −30 mol%
Up to 95% X OAc O H X = CH 2 , NTs
X N H 1,2 1,2
Pd + X O H 1,2 up to 95% up to 13 : 1 d.r. 5 mol% Pyrrolidine Pd(Ph 3 ) 4 5 mol%
Pyrrolidine 40 mol%
Proposed intermediate (a) Tsuji-Trost π-allyl palladium as electrophiles N R'' R' [M]
Proposed intermediate O H X R X = C(CO 2 R), C(SO
2 Ph), CCH
2 OR R = alkyl Cu(OTf) 2 6 mol% (R)-DTBM-MeOBIPHEP 15 mol%
X O H R CyNH
2 Enantioselective intramolecular carbocyclization 43–92% up to 94% e.e. Enantioselective cascade Michael addition-carbocyclization O R + NC R' N H Ar Ar OTMS
Ar = 3,5-(CF 3 ) 2 C 6 H 3 10 mol% Cu(OTf) 5 mol% PPh
3 20 mol%
R' CN RR CHO R = alkyl, aryl; R ′ = CO 2
up to 97% up to 99% e.e. up to 20 : 1 d.r.
S R X + Bn O 2) NaBH
4 R Bn OH R Bn OH +
anti NH Ar Ar OTMS Ru Ru
S Cl Cl *Cp Cp*
R = Ph, X = OH, 90%, 2.2 : 1 syn:anti, 96% e.e. syn 87% e.e. anti Ar = 3,5-(CF 3 ) 2 C 6 H 3 CuOTf/rac-BINAP R = 1-naphthyl, X = OC(O)C 6 F 5 , 54%, 3.8:1 syn:anti, 99% e.e. syn 97% e.e. anti [M]
R H N X Bn
1) Metal 5 mol% 5 mol% Proposed intermediate (c) Propargyl alcohol or benzoates as electrophiles Internal alkynes Ar 1 OH + Bn O 1) 2) NaBH 4 Ar 1 Bn OH Ar 1 Bn OH + syn anti Ar 2 Ar 2 Ar 2 18 −94%, up to 1.2 : 1 syn:anti, up to 97% e.e. syn 97% e.e. anti 20 mol%
InBr 3 N N H O Bn 20 mol%
Ar 1 HO Ar 2 InBr 3 Ar 1 HO Ar 2 InBr 3
intermediates Scheme 26.4 (a–c) Selected examples of cooperative enamine addition into metal-activated electrophiles. Living ROP Immortal ROP = Monomer = Ae initiator (living ROP)/catalyst (immortal ROP) = External protic transfer agent (alcohol, amine, etc.) n growing polymer chains one chain per metal initiator chain length = m/n one growing polymer chain p −1 dormant chains p chains per metal catalyst chain length = m/p n × initiator p × transfer agent 1 × catalyst m × monomer Scheme 28.5 Illustrative comparison of the living and immortal ROP processes. Figure 29.4 Crystal structure of [Me 4 N][Ag(SnB 11 H 11 )] and its metal organization group. Figure 29.5 View along the plane a–b of {[Me 4
4 [Ag
4 (SnB
11 H 11 ) 4 (DIB) 6 /2 ] } n . The solvents into the material porous were not represented for the sake of clarity. Figure 29.6 Crystal structure and packing of water-soluble Ru–Ag-backbone organometallic polymer. (a) (b)
(c) Figure 30.16 Space-fill representation of 14 (b) and 13 (c). H atoms are not indicated and crystallized water molecules are indicated as red balls. In (a), the water molecules have been fictionally removed, evidencing the space they occupy in 13. 13 14 15 Figure 30.17 Samples of compounds 13–15. 100 nm 50 nm
10 nm (a)
(b) (c)
(d) Figure 31.11 (a) SEM image of nanostars. (Inset), TEM image of a single star. (b) TEM image of porous nanocubes, obtained with dodecylamine/lauric acid surfactants. (c), (d) 3D reconstruction of the nanocubes obtained from electron tomography study, the defects embedded within the objects are represented in blue, and the outer surface of the cubes are in light violet. (b) (a)
(c) H 1 H 2 [010] [100] [001]
10 nm 15 15 20 25 30 35 40 45 20 25 30 35 40 45 20 30 40 z (nm)
x (nm) y (nm) 0 0.1 0.2 0.3
0.4 0.5 m 2 0.6
0.7 0.8
0.9 1
(a) TEM image of a 30 nm nanocube. (b) Mapping of the induction field obtained from electronic holography. (c) 3D visualization of the magnetic moment simulated within the nanocube. 3 4 Figure 32.3 Molecular structure of [Ba {(μ-ddbfo) 2 InMe 2 } 2 ] (3) and [Ba {(μ-ddbfo) 2 ZnEt
} 2 ] (4) (the H atoms are omitted for clarity). Figure 32.5 Molecular structure of [Ca 4 Ti
(μ 6 −O)(μ 3 , η
2 −OCH
2 CH 2 OCH 3 ) 8 (η−OCH
2 CH 2 OCH 3 ) 2 Cl l4 ] (the H atoms are omitted for clarity) and its Ca 4 Ti
(μ 6 −O)O 8 Cl 4 core. Carbon source dissociates in the gas phase into C
n (n ≥ 1) fragments (i) Carbon source interacts with catalyst surface
(ii) Carbon source dissociates into fragments (C 2
3 , C
4 etc.), entering the gas phase (iii) Fragments can adsorb back onto catalyst surface (iv) Growth via adsorbed C n (n ≥ 1) fragments (v) Growth via dissolution of C 1 species
Support Metal
Carbon precursor Carbon fiber/tube Figure 33.7 Proposed mechanism for CNT/F growth via carbon fragments. (i) Carbon source adsorbs onto the surface of the catalyst particle. (ii) Carbon source fragments on the catalyst and is released into the gas phase, or (iii) gas-phase fragments are readsorbed onto the catalyst surface. (iv) Growth of CNT/F from adsorbed carbon fragments. (v) Base growth mechanism as proposed by Baker [7]. Reprinted from Reference 7b. Copyright 2012, with permission from Elsevier.
R R R R + − − + 400 −20 −4 −2 0 2 4 20 0
(mdeg)
(mdeg)
−2 −1 −10 10 0 0 1 2
(mdeg)
(mdeg)
450 500
Wavelength (nm) 550
600 400
450 500
Wavelength (nm) 550
600 400
450 500
Wavelength (nm) 550
600 400
450 500
Wavelength (nm) 550
600 2a 2c 2d 2b (a) (b) Figure 34.2 (a) Schematic top view of the four sectors of the plane tangent to the attacked double bond with the respective sign. (b) CD spectra of both enantiomers of several cis-[60]fulleropyrrolidines (see Scheme 34.9): blue line represents (2R,5R) enantiomers obtained from Ag(I)/(–)BPE and the red line (2S,5S) enantiomers synthesized using Cu(II)/Fesulphos. + +
− 400
−20 0
(mdeg) 20
450 Wavelength (nm) 475 500
Ag(I)/(-)-BPE Cu(II)/Fesulphos MeO 2
H N Ar MeO 2 C N H Ar Figure 34.3 Absolute configuration assigned for both cis-2-carboximethyl-5-(p-methoxyphenyl)pyrrolidino[3,4:1,2][60]fullerene enan- tiomers using the sector rule.
(a) (b)
Figure 35.11 Crystal cell and packing structure of 15: (a) top and (b) side views. H atom is omitted for clarity. 5 10 15 20 2
25 30
5 10 15 20 2
25 30
Experimental 1 Experimental 2 i Pr
Pr
Pr
Pr
Pr
Pr
Pr
Pr Me
Br Br Br Br N N N N Ni Ni (a)
(b) Figure 37.4 Syntheses and characterization of complexes derived from (a) 1 and (b) 2. FTO TiO
2 Dye
Electrolyte Counter
electrode D + /D* 2 CB 5 7 6 1 4 D + /D
OC 3
3 − I − e V Figure 38.1 The construction of a dye-sensitized solar cell (DSSC) and its operating principle. D, Dye; CB, conduction band of TiO 2 ;
max , maximum voltage. h ν *P D M ox H 2 O P D M ox Photon capture/absorption Charge separation Charge transfer
“C1 or C1+” Energy
storage CO 2 P D + M red
P − D + M ox O 2
Constitutional elements of a device for the photochemical reduction of CO 2 in water under solar light irradiation. 1.8 1.6
1.4 1.2
1.0 0.8
0.6 0.4
0.2 0.0
0 2 4 6 8 Time (h) 10 12 14 16 18 20 Eq. H 2 [Rh(COD)Cl] 2 RhCl
3 RuCl
3 Ru(COD)Cl 2 Ni(COD)
2 Pd(DBA)
2 NiCl
2 Ni 2 B No catalyst Figure 40.10 Hydrogen evolution from AB-decomposition at 65 ◦ C catalyzed by different metal-catalyst precursors in [BMIM][Cl]. Reproduced from Reference 16 with permission of The Royal Society of Chemistry. 1 4 8 12 Days of treatment 16 20
2 3 4 Tumor volume cm 3 Tumor weight NaCI LNC
LNCs LNC-FcdiOH DSPE-m-PEG2000-LNC-FcdiOH DSPE-mPEG LNCs 0 1000
2000 3000
2408 1458
1071 33 Injection of 1.5 × 10
6 9L cells into rat flank D0 D6 Twice a week D25
Intravenous injection of LNCs loaded with Fc- diOH(400 μL, 2.4 mg/rat) Measurement of the tumor volume Animal sacrifice (tumor weight) Figure 42.12 Intravenous injection of two different sorts of LNC in ectopic tumors. 0 0
20 30 40 50 Days after 9L cell implantation 60 70
90 100
110 20 40 60 80 100 % Survival Control
Blank LNCs Chemotherapy (CED Fe-diOH-LNCs 0.36 mg/rat) Radiotherapy (CED Blank-LNCs + 3 × 6 Gy)
Chemoradiotherapy (CED Fe-diOH-LNCs 0.36mg/rat + 3 × 6 Gy) Median survival time (range) 25 (23–27) 25 (21–30) 27 (24–32) 33 (29–44) 40 (32–100) (two long-term survivors) Figure 42.13 Kaplan–Meier survival plots. H 2 N(CH 2 ) 2 NH 2
8 5 NC Carbon Rhenium Nitrogen
Oxygen Sulphur
Boron Scheme 44.2 Reactions of fac-[Re {κ 3
2 B (tim Me ) 2 }(CO) 3 ]. (5) with ethylenediamine and cyclohexyl isonitrile (tim Me = 2-mercapto- 1-methylimidazolyl) [38, 39]. PPh
3 pzH
pzH 6 9 10 11 Carbon
Rhenium Nitrogen
Oxygen Sulphur
Boron Phosphorous Scheme 44.3 Reactions of fac-[Re {κ 3
3 B (tim Me )}(CO)
3 ]. (6) with triphenylphosphine and pyrazole (tim Me = 2-mercapto-1- methylimidazolyl) [40, 41]. Carbon Rhenium
Nitrogen Oxygen
Sulphur Figure 44.3 Selected examples of Re(I) tricarbonyl complexes with tridentate Werner-type ligands [14–18]. 17 Carbon
Rhenium Nitrogen
Oxygen Sulphur
Boron Figure 44.10 Molecular structure of a dihydrobis(mercaptoimidazolyl)borate Re(I) tricarbonyl complex containing two arylpiperazine pharmacophores [74]
21a 99m
Tc-MDP Figure 44.13 Planar whole-body gamma camera images of rats injected with complex 21a and 99m Tc-MDP at 2 h p.i. Reproduced with permission from The Royal Society of Chemistry. Figure 45.4 Structures of the cationic E- (a) and Z-isomers (b) of [Ru II (p-cymene)(L2c)Cl] + . Atoms are depicted in black (carbon), blue (nitrogen), red (oxygen), green (chlorine), magenta (ruthenium). Hydrogens and the anion (Cl − ) were omitted for clarity. Figure 45.5 Structures of the protonated paullone ligand HL1a + with an intramolecular hydrogen bond O–H · · · N (a) and ruthenium- arene complex cation [Ru(p-cymene)(L1a)Cl] + (b). Atoms are depicted in black (carbon), cyan (hydrogen), blue (nitrogen), red (oxygen), green (chlorine), magenta (ruthenium), and brown (bromine). Figure 45.6 X-ray structure of the paullone ligand L2d, bearing a TEMPO free-radical unit. Atoms are depicted in black (carbon), cyan (hydrogen), blue (nitrogen), red (oxygen).
Figure 45.7 Structures of the Cu(II) complexes of the paullone ligand L1d (a) and the related indoloquinoline-based ligand L6l (b). While the paullone backbone is considerably folded, the indoloquinoline backbone is planar. Non-labeled atoms represent carbon atoms. 1 2 0 25 μm Figure 46.3 Confocal image of macrophage (J777A.1) showing nucleus (1) with yeast cell-wall particles (2). Fe OH OH −0.2 0 0.2 0.4 0.6
0.8 0 0.1 0.2 0.3
0.4 0.5
0.6 I ( μ A) E (V vs SCE) + Pyridine Cytotoxic MeOH – 100 mV/s O 1
2 Fe −0.2 0 0.2
0.4 0.6
0.8 0 0.1 0.2 0.3
0.4 0.5
0.6 I ( μ A) E (V vs SCE) Not cytotoxic + Pyridine Fe OH OH MeOH – 100 mV/s O 1
1 (5) (6) (4) (a)
(b) Figure 47.2 Typical cyclic voltammograms of cytotoxic (b) and noncytotoxic (a) ferrocifens (2 mM in 0.1 M Bu 4 NBF
4 /MeOH) obtained in the absence and the presence of pyridine used as a base model. Electrode: Pt, 0.5 mm diameter; scan rate 0.5 V/s. (a)
(b) Figure 48.5 HOMO (a) and LUMO (b) of the compound I c. (a) (b)
Figure 48.8 LUMOs of the methoxy derivative V a (a) and the methylester derivative V e (b). 0.4 (a)
(b) 0.2
0.0 −0.2
−0.4 −0.6
E (v) versus Fc +/0
5 μ A 0.4 0.2 0.0
−0.2 −0.4
−0.6 E (v) versus Fc +/0
5 μ A
Cyclic voltammograms of (a) [ (C 5 Me 5 )Ir(Qa)] and (b) [(C 5 Me 5 )Ir(Qx)] in CH 2 Cl 2 /0.1 M Bu 4 NPF
6 at different scan rates. 0.6 0.4
0.2 0.0
−0.2 −0.4 −0.6 −0.8 −1.0 E (v) versus Fc +/0
5 μ A 0.4 (a) (b)
0.2 0.0
−0.2 −0.4
−0.6 E (v) versus Fc +/0
2.5 μ A
Cyclic voltammograms of (a) [ (C 5 Me 5 )Rh(Qy)] and (b) [(C 5 Me 5 )Rh(Qa)] in CH 2 Cl 2 /0.1 M Bu 4 NPF
6 at different scan rates. −2.0
−1.0 0.0
+1.0 E (V vs SCE) (a)
(b) O P Figure 51.10 Cyclic voltammetric profiles recorded at a platinum electrode in toluene-acetonitrile (4:1) solution of (a) Dy@C 82 and
(b) Dy@C 82 [CCH(COOMe) 2 PPh
3 ]. Scan rate: 0.05 V/s. (a) Adapted from Reference 25; (b) adapted from Reference 19. The optimized structure of Dy@C 82
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