Excited States and Reactive Intermediates

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Author Index C l a r k , Robin, J . Η., 57 Cohen, Susan L., 236 E n d i c o t t , John F., 85 E n g l i s h , Ann M., 150 F o r d , P e t e r C , 197 Gao, P., 135 G e w i r t h , Andrew Α., 236 Godber, John, 212 G o s z t o l a , D., 135 Gray, Harry B., 166 Güdel, Hans U. 1 Haspelagh, L., 12 H e n d r i c k x , M., 12 Hennig, H., 104 Kokkes, M. W., 66 K u n k e l y , H., 120 L e i , Y a b i n , 85 L e s s a r d , Ronald B., 85 M a r s h a l l , Janet L., 166 Mauk, A. G r a n t , 150 McLendon, George, 150 M i l l e r , John R., 150

Oskam, A., 66 O z i n , G e o f f r e y Α., 212 P a t t e r s o n , M. L., 135 Rehorek, D., 104 Ryu, Chong K u l , 85 S c h a f f l , S., 120 Schmidtke, Hans-Herbert, 23 Siraolo, Ken, 150 Solomon, Edward I . , 236 Stiegman A l b e r t E., 166 S t u f k e n s , D. J . , 66 T a d a y y o n i , Μ. Α., 135 T a r a i l a r a s a n , R., 85 T a y l o r , Karen, 150 T r o g l e r , W i l l i a m , C , 177 T u t t , Lee, 39 Vanquickenborne, L. G., 12 V o g l e r , Α., 120 Weaver, M. J . , 135 Wink, D a v i d , 197 Yang, Y. Y., 39 Z i n c k , J e f f r e y I . , 39

Subject Index A

Absorbâtes, e f f e c t o f s u r f a c e i n t e r a c t i o n , 138 A b s o r p t i o n a t e l e c t r o d e s , SERS m o n i t o r i n g , 135-147 Absorption spectra c o o r d i n a t i o n compounds, 25,29,31 c y a n o m e t a l l a t e s , 110,111f I r - p h o s p h i n e complexes, 205-209 i r o n - c a r b o n y l complexes, I 8 6 , l 8 9 f m e t a l - c a r b o n y l complexes, 67,69f p h o t o l y t i c products o f m e t a l - c a r b o n y l complexes, 70,74f p l a s t o c y a n i n , 237,240f Rh-phosphine complexes, 198-203 techniques t o obtain high q u a l i t y , 24 t r a n s i t i o n metal complexes, 42-43 Absorption s p e c t r a — S e e also S i n g l e - c r y s t a l a b s o r p t i o n spectrum A c i d , e f f e c t on d o u b l e t e x c i t e d s t a t e s , C r ( I I I ) complexes, 94,98f A c t i v a t i o n energy, b i o l o g i c a l e l e c t r o n t r a n s f e r , 151-154f

A d s o r b a t e s , o u t e r - and i n t e r - s p h e r e , 137 Ammine complexes p h o t o p h y s i c a l p r o p e r t i e s , 89 SERS v s . e l e c t r o c h e m i s t r y , 138-140 A n t i f e r r o m a g n e t i c o r b i t a l exchange parameters, C r ( I I I ) diraers, 7 Arhennius p l o t , e l e c t r o n - t r a n s f e r k i n e t i c s , cytochrome c d e r i v a t i v e s , 155,157,158f Arrhenius a c t i v a t i o n energies, C r ( I I I ) complexes, 93,96

Β

Back e l e c t r o n t r a n s f e r — S e e E l e c t r o n transfer Back e l e c t r o n - t r a n s f e r r a t e , c y a n o m e t a l l a t e s , 116 Band a n a l y s i s , e x c i t e d - s t a t e s t r u c t u r e , 24,25 Base, e f f e c t on d o u b l e t e x c i t e d s t a t e s , C r ( I I I ) complexes, 94,98f

Lever; Excited States and Reactive Intermediates ACS Symposium Series; American Chemical Society: Washington, DC, 1986.

269

INDEX

Bending d i s t o r t i o n s , e x c i t e d - s t a t e , raetal-nitrosyl complexes, 50 B i o l o g i c a l e l e c t r o n t r a n s p o r t , 150 Biological electron-transfer r e a c t i o n s , i n t r a m o l e c u l a r , 161-163 Biological electron-transfer reactions—See Electron transfer B l u e copper c e n t e r i n p l a s t o c y a n i n , s p e c t r a l p r o p e r t i e s , 236,238f,239f Bond l e n g t h changes, t u n g s t e n - c a r b o n y l complexes, 45-46,48 Bond l e n g t h s and s t r u c t u r e , p l a s t o c y a n i n , 237-240 Bonding o r b i t a l s — S e e M o l e c u l a r orbitals Bridging pyrophosphite—See Diphosphonate

C

C a r b o n y l complexes, p h o t o d i s s o c i a t i o n , 182-186 Carbonyl e l e c t r o o x i d a t i o n , I45,l46f Carbonyl-chromium c o m p l e x e s — S e e Chromium-carbonyl complexes Carbonyl-cobalt complexes—See Cobalt-carbonyl complexes Carbonyl-iron complexes—See I r o n - c a r b o n y l complexes Carbonyl-metal complexes—See M e t a l - c a r b o n y l complexes Carbonyl-tungsten complexes—See T u n g s t e n - c a r b o n y l complexes C a t a l y s i s c h e m i s t r y , Rh- and I r - p h o s p h i n e complexes, 197-210 Chain complexes, d i p h o s p h o n a t e - p l a t i n u m , 59 Charge t r a n s f e r , m e t a l - c a r b o n y l complexes, 75,78 Charge-transfer e x c i t a t i o n s , C r ( I I I ) complexes, 12-22 Charge-transfer t r a n s i t i o n s g e n e r a l c o n s i d e r a t i o n s , 16-19 m e t a l - c a r b o n y l complexes, 66-83 Chelates, unsaturated, i n t r a n s i t i o n m e t a l complexes, 177-194 Chemiluminescence, induced by e l e c t r o n t r a n s f e r , 121-122 Chemiluminescence—See a l s o E l e c t r o g e n e r a t e d chemiluminescence Chromium(II) complexes, EPR s p i n probe, 225-227 Chromium(III) complexes c h a r g e - t r a n s f e r t r a n s i t i o n s , 12-22 e x c i t e d - s t a t e l i f e t i m e s , 85-99 s p e c t r o s c o p y o f e x c i t e d s t a t e s , 1-11

Chromium-ammine complexes i r r e v e r s i b l e r e d u c t i o n s , 144 p h o t o p h y s i c a l p r o p e r t i e s , 89 Chromium-carbonyl complexes, e l e c t r o l y s i s , 128-129,130f C h r o m i u m - p o l y p y r i d y l complexes, 89 C l u s t e r complexes, v a l e n c e e l e c t r o n s , 63 C o b a l t complexes, p h o t o c h e m i s t r y , 178-182 Cobalt loading of z e o l i t e s , neutron a c t i v a t i o n a n a l y s i s , 213»214f Cobalt-ammine complexes, i r r e v e r s i b l e r e d u c t i o n s , 144 C o b a l t - c a r b o n y l complexes, l o a d i n g i n t o f a u j a s i t e s , 215-221 C o o r d i n a t i o n compounds e x c i t e d - s t a t e g e o m e t r i e s , 23-37 static spectral s e n s i t i z a t i o n , 104-118 Covalency photoelectron spectroscopic s t u d i e s , 258,264 p l a s t o c y a n i n , 248,251f,256,257f Cyano c o m p l e x e s — S e e C y a n o m e t a l l a t e s Cyanometallates a b s o r p t i o n s p e c t r a , 110,111f intervalance charge-transfer b e h a v i o r , 110,111f p h o t o c h e m i c a l b e h a v i o r , 113,116 photoinduced c a t a l y t i c system, 105,106f Cyanometallates—See also Transition m e t a l cyano complexes Cytochrome c d e r i v a t i v e s , photoinduced e l e c t r o n t r a n s f e r , 155-158 Cytochrome c p e r o x i d a s e / c y t o c h r o m e c derivatives, reaction r a t e s , 159,160f s t r u c t u r e , 159,160 Cytochrome c/cytochrome b5 complex e l e c t r o n - t r a n s f e r k i n e t i c s , 153 s t r u c t u r a l f e a t u r e s , 153,154f

D

Damping f a c t o r , t r a n s i t i o n m e t a l complexes, 43 Derealization c y a n o m e t a l l a t e s , IT t r a n s i t i o n parameters, 112-113 p l a s t o c y a n i n , 252-256 Density d i f f e r e n c e p l o t s f o r C r ( I I I ) complexes, 17-18 Dimer t r a n s i t i o n s , C r ( I I I ) d i m e r s , 3,6f


270

EXCITED STATES AND REACTIVE INTERMEDIATES

D i n u c l e a r complexes, a b s o r p t i o n s p e c t r a , 1-11 Diphosphonate complexes, e l e c t r o n - t r a n s f e r r e a c t i v i t y , 167 D i p h o s p h o n a t e - p l a t i n u m complexes electrogenerated chemiluminescence, 123 e l e c t r o n i c s p e c t r a , 61 structures, 6 l , 6 2 f type o f c h a i n , 59 Doublet e x c i t e d s t a t e C r ( I I I ) complexes, 85-99 role i n relaxation p r o c e s s , 96-97,98f Dynamic s p e c t r a l s e n s i t i z a t i o n , c o o r d i n a t i o n compounds, 107,108 Dynamic s p e c t r a l s e n s i t i z a t i o n — S e e also Spectral sensitization

Ε

Edge s p e c t r a , p l a s t o c y a n i n , 252,253f Electrochemical i n t e r f a c e s , molecular s p e c t r o s c o p i c p r o b e s , 135 Electrochemical reactions, i r r e v e r s i b l e and m u l t i s t e p , 143-147 E l e c t r o c h e m i c a l l y generated species i r o n - s u l f u r p r o t e i n s , 63-64 t r a n s i t i o n m e t a l complexes, 120-132 E l e c t r o c h e m i s t r y compared t o SERS, 138-140 E l e c t r o g e n e r a t e d chemiluminescence, t r a n s i t i o n m e t a l complexes, 123 Electrogeneration, of excited s t a t e s , 124-128 Electrolysis n i c k e l complexes, 129-131 r h e n i u m - p y r i d y l complex, 126-128 r u b i d i u m - b i p y r i d y l complex, 124-126 to p r e p a r e redox p a i r s , 122 without generation o f excited s t a t e s , 128-131 Electron d e r e a l i z a t i o n , t r a n s i t i o n metal cyano complexes, 140-143 E l e c t r o n paramagnetic resonance spectra b l u e copper p r o t e i n , 236,238f,250f c o b a l t complexes, 179 o r g a n o m e t a l l i c s p i n probes, 222-227 p l a s t o c y a n i n , 248,251f,256,257f E l e c t r o n s h i f t s upon c h a r g e - t r a n s f e r e x c i t a t i o n , C r ' I i J ) complexes, 17 Electron transfer, p r o t e i n - p r o t e i n , 151-153 Electron transfer—See also B i o l o g i c a l e l e c t r o n t r a n s f e r , Photoinduced electron transfer

E l e c t r o n - t r a n s f e r k i n e t i c s , cytochrome c/cytochrome b5 complex, 153,154f Electron-transfer reactions g e n e r a l d i s c u s s i o n , 120-121 i r i d i u m complexes, 166-175 p l a t i n u m complexes, 166-175 E l e c t r o n t r a n s p o r t , b i o l o g i c a l , 150 Electronic coupling i r o n - c y a n o complexes, 143 metal-dependent e f f e c t s , 157 E l e c t r o n i c spectra c a l c u l a t e d from Raman i n t e n s i t i e s , 44 t o determine v i b r a t i o n a l s t r u c t u r e , 24 Electronic spectra—See also Absorption spectra, Emission s p e c t r a , 24 E l e c t r o n i c s t r u c t u r e , metal i o n a c t i v e s i t e s , 236-264 E l e c t r o o x i d a t i o n , c a r b o n y l and i o d i d e , 145 Electrophotochemistry, 124 E m i s s i o n r e s u l t i n g from e x c i t e d s t a t e s , 124 Emission spectra c o o r d i n a t i o n compounds, 25,27-29,30f Cr(III)-amraine complexes, 89,92f luminescence from C r ( I I I ) complexes, 8,1 Of t e c h n i q u e s t o o b t a i n high q u a l i t y , 24 t r a n s i t i o n m e t a l complexes, 40-43 E m i s s i o n — S e e a l s o Chemiluminescence Energy p a t t e r n , c h a r g e - t r a n s f e r t r a n s i t i o n s , 19-22 Energy s p l i t t i n g s , i n C r ( I I I ) complexes, I 4 , 1 5 f Energy v s . d i s t o r t i o n diagram, m e t a l - c a r b o n y l complexes, 70,71f E P R — S e e E l e c t r o n paramagnetic resonance Exchange i n t e r a c t i o n s i n C r ( I I I ) dimer, 2-4 E x c i t a t i o n energy, c h a r g e - t r a n s f e r t r a n s i t i o n s , 20,22t Excited configuration, r e s u l t i n g s t a t e s , C r ( I I I ) complex, 19 Excited states C r ( I I I ) complexes, s p e c t r o s c o p y , 1-11 e l e c t r o g e n e r a t i o n , 124-128 redox p o t e n t i a l s , 166 t r a n s i t i o n m e t a l complexes, generated e l e c t r o c h e m i c a l l y , 120-132 Excited s t a t e s — S e e also Intervalence s t a t e , 57 Excited-state d i s t o r t i o n s c a l c u l a t e d from Raman i n t e n s i t i e s , 44


271

INDEX

Excited-state distortions—Continued c o r r e l a t e d t o photochemical r e a c t i v i t y , 48 m e t a l - n i t r o s y l complexes, 50 tungsten-carbonyl complexes, 41f,45-46 E x c i t e d - s t a t e geometries c o o r d i n a t i o n compounds, 23-37 t r a n s i t i o n m e t a l complexes, 39-55 Excited-state lifetimes, Cr(IIl5 complexes, 85-99 E x c i t e d - s t a t e Raman s p e c t r a , t r a n s i t i o n m e t a l complexes, 52-54

F

Faujasites cobalt loading, 213 IR s p e c t r a , 215-221 Faujasites—See also Zeolites F e r r o c e n e , o p t i c a l p r o p e r t i e s , 227-232 Flash photolysis cytochrome c d e r i v a t i v e s , 155,156f,158f I r - p h o s p h i n e complexes, 205-209 Rh-phosphine complexes, 198-203 F o u r i e r t r a n s f o r m IR s p e c t r a — S e e IR spectra

G

Geometrical d i s t o r t i o n s C r ( I I I ) complexes c a l c u l a t e d from quenching, 9,1 Of e f f e c t o f l i g a n d s , 95-96 excited states o f coordination compounds, 23-37 excited-state metal-nitrosyl complexes, 50 t r a n s i t i o n m e t a l complexes, 39-55 Ground-state wavefunction, p l a s t o c y a n i n , 248,251f,256,257f

H

H a l o c a r b o n s , r e a c t i v i t y w i t h I r and P t complexes, 171,174 Hartree-Fock c a l c u l a t i o n s , f o r c h a r g e - t r a n s f e r t r a n s i t i o n s , 20 High-resolution crystal spectra—See S i n g l e - c r y s t a l a b s o r p t i o n spectrum

Homolytic s p l i t t i n g , metal-metal bond, 73,78,79 H y d r o x i d e , e f f e c t on d o u b l e t e x c i t e d s t a t e s , C r ( I I I ) complexes, 9 4 , 9 8 f Hyperfine parameters, p l a s t o c y a n i n , 258,259t

I

I n t e r e l e c t r o n i c r e p u l s i o n energy, excited states i n Cr(III) complexes, 16,20,22 Intervalance charge-transfer energy, 110,112,1l4f Intervalence charge-transfer behavior c y a n o m e t a l l a t e s , 110,11f e f f e c t o f s o l v e n t , 110,111Γ e f f e c t on p h o t o c h e m i c a l r e a c t i o n s , 115 e f f e c t on s t a t i c s e n s i t i z a t i o n , 109-110 Intervalence t r a n s i t i o n s , platinum complexes, 58 Intramolecular b i o l o g i c a l electron-transfer reactions, 161-163 I n t r a m o l e c u l a r p r o t e i n redox r e a c t i o n s , comparisons, 161 I n t r a z e o l i t e chemistry, C r ( I I ) - o r g a n o c y c l i c complex, 225 I n t r a z e o l i t e organometallics, i n t e r n a l v e r s u s e x t e r n a l confinement o f metal g u e s t s , 212-233 I o d i d e e l e c t r o o x i d a t i o n , 145 IR bands, p h o t o l y t i c p r o d u c t s o f metal-carbonyl complexes, 7 0 , 7 2 f , 7 4 f , 8 0 , 8 l f IR c i r c u l a r d i c h r o i s m s p e c t r a , b l u e copper p r o t e i n , 237,238f IR s p e c t r a , f a u j a s i t e s , 215-221 I r i d i u m complexes e l e c t r o n - t r a n s f e r r e a c t i o n s , 166-175 p h o t o c h e m i s t r y , 166-175 I r i d i u m - p h o s p h i n e complexes, r e a c t i o n s k i n e t i c s , 203-209 I r o n - c a r b o n y l complexes, p h o t o d i s s o c i a t i o n , 182-186 Iron-cyano complexes, SER s p e c t r a , 140-143 I r o n - o r g a n o c y c l i c complexes, o p t i c a l p r o p e r t i e s , 227-232 I r o n - s u l f u r p r o t e i n s , valence e l e c t r o n s , 63 I r r a d i a t i o n , cobalt complexes, 179,181-182


272


J

Jahn-Teller e f f e c t , Cr(III) complexes, 8-9

Κ

Kinetics—See

Reaction k i n e t i c s

L

Lifetimes, excited state—See Excited-state lifetimes Ligand e f f e c t , macrocyclic, e x c i t e d - s t a t e l i f e t i m e s , 94 Ligand f i e l d c a l c u l a t i o n s , p l a s t o c y a n i n , 248,251f Ligand f i e l d c o n s i d e r a t i o n s C r ( I I I ) complexes, 14-16 tungsten-carbonyl complexes, 47-48 Ligand s u b s t i t u t i o n r e a c t i o n s , t r a n s i t i o n m e t a l complexes, 131 Ligands ammine, 89, 138-140, 144 d i p h o s p h o n a t e , 59,167 e f f e c t on e x c i t e d - s t a t e d i s t o r t i o n s , 95-96 o x a l a t e , 188 phosphines, 78,178,197 p y r i d i n e , 89,126-128,167 L i n e a r - c h a i n complexes, 57-64 Luminescence from C r ( I I I ) complexes d e s c r i p t i o n , 1-2,4f e m i s s i o n s p e c t r a , 8,10f Luminescence s p e c t r a — S e e E m i s s i o n spectra

M

Macrocyclic ligand e f f e c t , e x c i t e d - s t a t e l i f e t i m e s , 94 Mechanism c a t a l y s i s c h e m i s t r y o f Rh- and I r - p h o s p h i n e complexes, 197-210 organometallics, p h o t o r e a c t i o n s , 186-188 M e c h a n i s m — S e e a l s o R e a c t i o n mechanism M e t a l d i m e r s , p h o t o c h e m i s t r y , 166 M e t a l g u e s t s , confinement i n intrazeolite o r g a n o m e t a l l i c s , 212-233

Metal ion a c t i v e s i t e s , e l e c t r o n i c s t r u c t u r e , 236-264 Metal loading, z e o l i t e s with o r g a n o m e t a l l i c s , 212-233 M e t a l - c a r b o n y l complexes, p h o t o c h e m i s t r y , 66-83 Metal-cyano c o m p l e x e s — S e e Cyanometallates Metal-dependent e f f e c t s , on e l e c t r o n i c c o u p l i n g , 157 M e t a l - m e t a l bond, h o r a o l y t i c s p l i t t i n g , 73,78,79 M e t a l - m e t a l bonded complexes, p h o t o c h e m i s t r y , 66 M e t a l - n i t r o s y l complexes, e x c i t e d - s t a t e bending d i s t o r t i o n s , 50 M e t a l l a c y c l e s , p h o t o c h e m i s t r y , 178 Metallacycles—See also Organometallics Metallocytochrome c d e r i v a t i v e s , r e a c t i o n r a t e s , 159,l60f MIME—See M i s s i n g mode e f f e c t M i s s i n g mode e f f e c t , t u n g s t e n - c a r b o n y l complexes, 49-50 Mitochondrial electron-transport c h a i n , 150 M i x e d - v a l e n c e compounds, p h o t o c a t a l y t i c systems, 104-118 Molecular o r b i t a l s C r ( I I I ) complex, 1 2 - 1 3 f m e t a l - c a r b o n y l complexes, 67 p l a s t o c y a n i n , 241-248 M o l e c u l a r s p e c t r o s c o p i c probes, e l e c t r o c h e m i c a l i n t e r f a c e s , 135 Mononuclear complexes, a b s o r p t i o n s p e c t r a , 1-11

Ν

Neutron a c t i v a t i o n a n a l y s i s , c o b a l t loading o f z e o l i t e s , 213,2l4f N i c k e l complexes, e l e c t r o l y s i s , 129-131 N i c k e l - o x a l a t e complexes, photochemistry, 188-191 N i t r o s y l complexes—See M e t a l - n i t r o s y l complexes, 50 NMR s p e c t r a , p h o t o r e a c t i o n s o f P t o x a l a t e complexes, I 8 8 , l 8 9 f

0 Olefins photocatalytic hydrogénation, 51-52,54f


INDEX

273

Olefins—Continued photocatalytic reactions with i r o n - c a r b o n y l complexes, 186 One-dimensional s p e c i e s , 57-64 O p t i c a l r e f l e c t a n c e probes, o r g a n o m e t a l l i c s , 227-232 O p t i c a l s p e c t r a , b l u e copper p r o t e i n , 236,238f,240f O r b i t a l c h a r a c t e r i s t i c s , lowest excited state, tungsten-carbonyl complexes, 47 O r b i t a l density difference, i n c h a r g e - t r a n s f e r s t a t e s , 17-19 O r b i t a l energy diagram, Co complexes, 179,180f O r b i t a l exchange parameters o f C r ( I I I ) d i m e r s , s t r u c t u r a l and antiferromagnetic, 7 Orbital interactions, Cr(III) dimers, 3 O r g a n o m e t a l l i c complexes, l o a d i n g i n t o z e o l i t e s , 212-233 O r g a n o m e t a l l i c s p i n probes, e l e c t r o n paramagnetic resonance s p e c t r a , 222-227 Organometallics c y c l i c , p h o t o c h e m i s t r y , 178 o p t i c a l r e f l e c t a n c e probes, 227-232 p h o t o r e a c t i o n s , mechanism, 186-188 Organometallics—See also Metallacycles ORTEP, c o b a l t complexes, 179,180f Overlap p o p u l a t i o n s , t r a n s i t i o n metal complexes, 42-43 O x a l a t e complexes, p h o t o c h e m i s t r y , 188-191

Ρ

Palladium, addition of a l l y l compounds, 188 P a l l a d i u m - o x a l a t e complexes, p h o t o c h e m i s t r y , 188-191 pH, e f f e c t on d o u b l e t e x c i t e d s t a t e s , C r ( I I I ) complexes, 94,98f Phosphine complexes, r e a c t i o n k i n e t i c s , 198-209 Phosphines trisubstituted as l i g a n d s , 78,197 p h o t o c h e m i s t r y , 178 P h o t o c a t a l y t i c hydrogénation o f o l e f i n s , 51-52,54f Photocatalytic reactions d e s c r i p t i o n s , 104-105,106f

Photocatalytic reactions—Continued effect of spectral s e n s i t i z a t i o n , 105 i r o n - c a r b o n y l complexes w i t h o l e f i n s and s i l a n e s , 186 P h o t o c a t a l y t i c systems, mixed-valence compounds, 104-118 P h o t o c h e m i c a l mechanism, charge transfer i n metal-carbonyl complexes, 75,78 Photochemical r e a c t i o n s c y a n o m e t a l l a t e s , e f f e c t o f IT e x c i t a t i o n , 115 t r a n s i t i o n metal complexes, c l a s s i f i c a t i o n , 177 w i t h phosphines, m e t a l - c a r b o n y l complexes, 78-79 Photochemical r e a c t i v i t y correlated to excited-state d i s t o r t i o n s , 48 g e n e r a l d i s c u s s i o n , 23 m e t a l - n i t r o s y l complexes, 51 Photochemical s u b s t i t u t i o n r e a c t i o n s , t r a n s i t i o n metal complexes, 131 Photochemistry c y a n o m e t a l l a t e s , 113,116 I r complexes, 166-175 I r - p h o s p h i n e complexes, 205-209 m e t a l - c a r b o n y l complexes, 66-83 o x a l a t e complexes, 188-191 p l a t i n u m complexes, 166-175 Rh-phosphine complexes, 198-203 Photodissociation, iron-carbonyl complexes, 182-186 Photoelectron spectroscopic studies of c o v a l e n c y , 258-264 Photoinduced c a t a l y t i c system, c y a n o m e t a l l a t e s , 105,106f Photoinduced e l e c t r o n t r a n s f e r , cytochrome c d e r i v a t i v e s , 155-158 Photolysis c y a n o m e t a l l a t e s , 117 i n r i g i d media, m e t a l - c a r b o n y l complexes, 80-83 Photolytic products, metal-carbonyl complexes, 70-77 Photon f l u x f l u c t u a t i o n , c o o r d i n a t i o n compounds, 31,33-37 Photons as s c a v e n g e r s , IT e x c i t a t i o n o f c y a n o m e t a l l a t e s , 117 Photooxidative addition, h a l o c a r b o n s t o I r and P t complexes, 171-174 P h o t o p h y s i c a l p r o p e r t i e s , ammine complexes, 89 Photoreactivity, Pt-oxalate complexes, 191 P h o t o s u b s t i t u t i o n , CO by t r i p h e n y l p h o s p h i n e , 186, l 8 9 f



274

P i p e r i d i n e complexes, e x c i t e d - s t a t e g e o m e t r i e s , 39-55 P l a s t o c y a n i n , b l u e copper c e n t e r , s p e c t r a l p r o p e r t i e s , 236,238f,239f P l a t i n u m complexes e l e c t r o n - t r a n s f e r r e a c t i o n s , 166-175 p h o t o c h e m i s t r y , 166-175 resonance Raman s p e c t r o s c o p y , 57-64 Platinum complexes—See D i s p h o s p h a t e - p l a t i n u m complexes P l a t i n u m - o x a l a t e complexes p h o t o c h e m i s t r y , 188-191 s y n t h e s i s and p h o t o r e a c t i v i t y , 191 P o l y p y r i d y l complexes, e f f e c t o f s o l v e n t s on e x c i t e d - s t a t e l i f e t i m e s , 89 P o p — S e e Diphosphonate P o t e n t i a l energy, p h o t o c h e m i c a l reactions of cyanometallates, 113,1l4f P o t e n t i a l energy c u r v e s , c o o r d i n a t i o n compounds, 25,26f Protein-protein electron transfer, t h e o r i e s , 151-153 Proteins i r o n - s u l f u r , 63 redox r e a c t i o n s , i n t r a m o l e c u l a r , comparisons, 161 P y r i d i n e , as l i g a n d , 89 P y r i d i n e complexes e l e c t r o l y s i s , 126-128 e x c i t e d - s t a t e g e o m e t r i e s , 39-55 Pyridinium cations, r e a c t i v i t y w i t h I r and P t complexes, 167 Pyrophosphite, b r i d g i n g — S e e Diphosphonate

Q

Quantum y i e l d , p h o t o s u b s t i t u t i o n o f CO by t r i p h e n y l p h o s p h i n e , I 8 6 , l 8 9 f Quenching electron transfer, I r complexes, 167,I69f,170t,173 used t o c a l c u l a t e g e o m e t r i c a l d i s t o r t i o n s , 9,10f

R

Raman i n t e n s i t i e s , used t o c a l c u l a t e e x c i t e d - s t a t e d i s t o r t i o n s and e l e c t r o n i c s p e c t r a , 44 Raman s p e c t r a e x c i t e d - s t a t e , t r a n s i t i o n metal complexes, 52-54

Raman s p e c t r a — C o n t i n u e d p l a t i n u m complexes, 58 t r a n s i t i o n m e t a l complexes, 44 Raman s p e c t r o s c o p y — S e e a l s o Surface-enchanced Raman spectroscopy Rate c o n s t a n t s c y a n o m e t a l l a t e s , 116 r e a c t i o n s o f Rh-phosphine complexes, 203 R e a c t i o n k i n e t i c s , Rh- and I r - p h o s p h i n e complexes, 197-210 R e a c t i o n mechanism, m e t a l l a c y c l e p h o t o c h e m i s t r y , 178-182 R e a c t i o n mechanism—See a l s o Mechanism Reaction rates cytochrome c p e r o x i d a s e / c y t o c h r o m e c d e r i v a t i v e s , 159,l60f metallocytochrome c d e r i v a t i v e s , 159,l60f Reactive excited s t a t e s , e l e c t r o g e n e r a t i o n , 126 Redox c a t a l y s i s , l e a d i n g t o chemiluminescence, 121-122 Redox c o u p l e s , surface-enhanced Raman s p e c t r o s c o p y , 138,140-143 Redox p a i r s , e l e c t r o l y s i s , t o p r e p a r e , 122 Redox p o t e n t i a l s , e x c i t e d s t a t e s , 166 Redox p r o c e s s e s a t m e t a l - s o l u t i o n i n t e r f a c e s , SERS, 135-147 Redox r e a c t i o n s , i n t r a m o l e c u l a r p r o t e i n , comparisons, 161 Reduction p o t e n t i a l s c o b a l t complexes, 179 IT t r a n s i t i o n s i n c y a n o m e t a l l a t e s , 112 R e d u c t i o n s , i r r e v e r s i b l e , ammine complexes, 144 Relative frequencies, cumulative, f o r photons, 3 3 , 3 4 f R e l a x a t i o n energy, c h a r g e - t r a n s f e r t r a n s i t i o n s , 17 R e l a x a t i o n mechanism, g e n e r a l features, 97,99 Relaxation process, r o l e o f doublet e x c i t e d s t a t e , 96-97,98f Relaxation rates, excited states of C r ( I I I ) complexes, 88-95 R e p u l s i o n energy, c h a r g e - t r a n s f e r t r a n s i t i o n s , 20,22t Resonance Raman s p e c t r a m e t a l - c a r b o n y l complexes, 67,69f p l a t i n u m complexes, 57-64 R h e n i u m - p y r i d y l complex, e l e c t r o l y s i s , 126-128 Rhodium-phosphine complexes, r e a c t i o n k i n e t i c s , 198-203 Rubidium-ammine complexes, SERS v s . e l e c t r o c h e m i s t r y , 138-140


INDEX

275

R u b i d i u m - b i p y r i d y l complex, e l e c t r o l y s i s , 124-126

S

S E R S — S e e Surface-enhanced Raman spectroscopy Silanes, t r i a l k y l , photocatalytic reactions with iron-carbonyl complexes, 186 S i l i c a , use i n s y n t h e s i s o f surface-attached oxalate complexes, 192,193 S i n g l e - c r y s t a l absorption spectra C r ( I I I ) d i m e r s , 3,5f p l a s t o c y a n i n , 252,253f temperature dependence, 3,5f Size exclusion chemistry, Cr(II) o r g a n o c y c l i c complex, 225 Solvents e f f e c t on e x c i t e d - s t a t e l i f e t i m e s i n C r ( I I I ) complexes, 89 e f f e c t on i n t e r v a l a n c e charge-transfer b e h a v i o r , 110,11f S p e c t r a l p r o p e r t i e s , b l u e copper center i n p l a s t o c y a n i n , 236,238f,239f S p e c t r a l s e n s i t i z a t i o n , e f f e c t on p h o t o c a t a l y t i c r e a c t i o n s , 105 Spectral s e n s i t i z a t i o n — S e e also Static spectral sensitization, Dynamic s p e c t r a l sensitization Spectroscopic data, platinum complexes, 60 Spectroscopic s t u d i e s , blue copper, 236-264 S p i n p r o b e s , o r g a n o m e t a l l i c , EPR s p e c t r a , 222-227 S t a t e e n e r g i e s , C r ( I I I ) complexes, g e n e r a l d i s c u s s i o n , 86,87f States—See Excited states S t a t i c s e n s i t i z a t i o n , effect of intervalence charge-transfer b e h a v i o r , 109-110 Static spectral sensitization c o o r d i n a t i o n compounds, 104-118 mechanism, 107,109 Static spectral sensitization—See also Spectral sensitization S t r u c t u r a l f e a t u r e s , cytochrome c/cytochrome b5 complex, 153,154f S t r u c t u r a l o r b i t a l exchange parameters, C r ( I I I ) d i m e r s , 7 S t r u c t u r e , cytochrome c p e r o x i d a s e / c y t o c h r o m e c, 159,160

Substitution reactions, transition metal complexes, 131 S u l f u r - i r o n p r o t e i n s , 63 Superexchange i n C r ( I I I ) d i m e r s , 2 Surface i n t e r a c t i o n , e f f e c t of a d s o r b a t e s , 138 Surface-bound P t - o x a l a t e complexes, 1 9 1 - 1 9 4 Surface-enchanced Raman s p e c t r o s c o p y compared t o e l e c t r o c h e m i s t r y , 138-140 d e t e c t i o n o f o u t e r - and i n n e r - s p h e r e absorbâtes, 137 t r a n s i t i o n m e t a l redox c o u p l e s , 138,140-143 Surface-enchanced Raman s p e c t r o s c o p y — S e e a l s o Raman spectroscopy Synthesis, platinum-oxalate complexes, 191

Τ

Temperature e f f e c t on e x c i t e d - s t a t e l i f e t i m e s , C r ( I I I ) complexes, 88-89,92f e f f e c t on p h o t o c h e m i c a l r e a c t i o n s , 78 Temperature dependence, s i n g l e - c r y s t a l a b s o r p t i o n spectrum, 3,5f Temperature-dependent component, r e l a x a t i o n mechanism, 97 T h i n - l a y e r e l e c t r o c h e m i s t r y , 63-64 T h i o e t h e r bonds, p l a s t o c y a n i n , 237 T h i o l a t e bonds, p l a s t o c y a n i n , 237 Time-dependent t h e o r e t i c a l t r e a t m e n t , emission spectra of t r a n s i t i o n m e t a l complexes, 42-43 Time-resolved emission s p e c t r a , c o o r d i n a t i o n compounds, 31,33-35 T r a n s i t i o n metal complexes c l a s s i f i c a t i o n o f photochemical r e a c t i o n s , 177 e x c i t e d - s t a t e g e o m e t r i e s , 39-55 generated e l e c t r o c h e m i c a l l y , e x c i t e d s t a t e s , 120-132 p h o t o c h e m i s t r y , 66-83 s u b s t i t u t i o n r e a c t i o n s , 131 T r a n s i t i o n m e t a l cyano complexes, e l e c t r o n d e r e a l i z a t i o n , 140-143 T r a n s i t i o n metal redox c o u p l e s , s u r f a c e - e n c h a n c e d Raman s p e c t r o s c o p y , 138,140-143 T u n g s t e n - c a r b o n y l complexes, excited-state distortions of, 4lf,45-46


276


V i b r o n i c s p e c t r a , d e f i n i t i o n , 23 V i s i b l e s p e c t r a — S e e Absorption spectra, Emission spectra Unsaturated c h e l a t e s , i n t r a n s i t i o n metal complexes, p h o t o c h e m i c a l r e a c t i o n s , 177-194 UV i r r a d i a t i o n , e f f e c t on P t complexes, 188, 190 UV s p e c t r a — S e e A b s o r p t i o n s p e c t r a , Emission spectra UV-photoelectron s p e c t r a , m e t a l - c a r b o n y l complexes, 67,68f UV-visible reflectance spectra, o r g a n o m e t a l l i c s , 227-232

W

Wavefunction, ground s t a t e , p l a s t o c y a n i n , 248,251f,256,257f W o l f f r a m s r e d type s a l t s , 58 Wolffrara's red type s a l t s — S e e a l s o P l a t i n u m complexes 1

X-ray c r y s t a l l o g r a p h i c s p e c t r a , b l u e copper p r o t e i n , 237,239f Valence e l e c t r o n s , c l u s t e r complexes, 63 Vanadium complex, EPR s p i n probes, 222-225 V i b r a t i o n a l a n a l y s i s , emission spectra o f C r ( I I I ) complexes, 8 V i b r a t i o n a l s t r u c t u r e , determined from e l e c t r o n i c s p e c t r a , 27

Z e o l i t e s , loading with organometallic complexes, 212-233 Zeolites—See also Faujasites

Production by Anne Riesberg Indexing by Janet S. Dodd Jacket design by Pamela Lewis Elements typeset by Hot Type Ltd., Washington, DC Printed and bound by Maple Press Co., York, PA


Excited States and Reactive Intermediates

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