Supporting Information for Design, Synthesis and Properties of Conformationally Fixed Semiquinone Monoradical Species

Transcription

1 Supprting Infrmatin fr Design, Synthesis and Prperties f Cnfrmatinally Fixed Semiquinne Mnradical Species David A. Shultz, Jseph C. Slp and Gary Washingtn Table f Cntents 1. General Experimental Methds 2 2. NMR Spectra f Characterized Cmpunds....4 a. 2'(2-Hydrxyprpyl)-5-t-butyl-3,4-dimethxybiphenyl (3)..4 b. 3-t-Butyl-9,9-dimethylflurene rthquinne (6).5 c. 3-t-Butyl-1,2-dimethxy-9-flurenne (8) 6 d. 3-t-Butyl-1,2-dihydrxy-9-flurenne (9) 7 e. 5-t -Butyl-2'-nitr-2,3-dimethxymethylenxybiphenyl (12)...8 f. 4-t-Butyl-2,3-dimethxymethylenxycarbazle (13a)...9 g. 2-t-butyl-3,4-dimethxymethylenxycarbazle (13b)..10 h. 9N-methyl-4-t -butyl-2,3-dimethxymethylenxycarbazle (14) 11 i. 9N-methyl-4-t-butyl-2,3-dihydrxycarbazle (15) 12 j. 9N-methyl-4-t -butylcarbazle rthquinne (16)..13 k. 1-Hydrxydibenzfuran (19). 14 l. 1-Methxydibenzfuran (20)..15 m. 2-Hydrxy-1-methxydibenzfuran (21) n. 1,2-Dimethxydibenzfuran (22) t-Butyl-1,2-dimethxydibenzfuran (23a).. 18 q. 8-t-Butyl-1,2-dimethxydibenzfuran (23b) r. 3-t-Butyl-1,2-dihydrxydibenzfuran (24a) s. 8-t-Butyl-1,2-dihydrxydibenzfuran (24b) 21 t. DFT Cmputatinal Parameters fr cmpunds 7, 10, 17, 25a and 25b 22 u. Cyclic Vltammagrams fr 6F7 and 16F17.29 S1

2 1. General Experimental Methds. General Methds fr Preparatin f Methxy and Methxymethyl Prtected t - Butylbiphenyls. In a 125 ml Keldahl flask equipped with a N2 adapter and stir bar was added 1 equivalent f the phenyl halide, 1 equivalent f 3-t -butyl-4,sbis(methxymethylenxy)phenylbrnic ester (r 3-t-butyl-4,S-dimethxyphenylbrnic ester), 5 ml% Pd(PPh3)4, dry THF (20-S0mL), EtOH (1-10 ml), and 2M Na2C03 (1-1S ml). A reflux cndenser was added, the reactin mixture purged lox with N2 and refluxed fr 24h. Fllwing filtratin thrugh celite, the slvent was remved by evapratin under reduced pressure, extracted with Et20, washed with saturated brine slutin, cncentrated, and subjected t radial chrmatgraphy (silica gel w/s-40% ether/pet ether gradient) t aff<?rdthe prduct. General Prcedures fr the Preparatin f Catechls: Methd A. T a 100mL rund bttm flask equipped with a stir bar was added the t-butylbis(methxymethylenxy)biphenyl (- 1-3 mml), cncentrated HCI (2mL), and methanl (SO-70mL). A reflux cndenser was attached, and the mixture refluxed fr 18h with stirring under N2,prtected frm light. The slvent was remved by evapratin under reduced pressure. The residue was taken up in CH2Ch, extracted with saturated brine, and the bttm rganic layer dried ver Na2S04. The slvent was evaprated t dryness t affrd the catechl. S2

3 General Prcedures fr the Preparatin f Catechls: Methd B. T a 125 ml Keldahl flask equipped with a Nz adapter and stir bar was added the t-butyl-dimethxybiphenyl (1 equivalent, mml), distilled CHzClz(-lOmL), purged 3X with Nz, and cled t -7SC. Then, a 1.0M slutin f BBr3(3 equivalents, mml), was added drpwise slwly t the reactin mixture, which was then allwed t warm t rm temperature and stir fr 20h under Nz, prtected frm light. The reactin mixture was quenched with ice, washed with saturated brine and extracted with tw loml prtins f CHzClz. The rganic layers were cmbined, dried ver NaZS04, and the slvent evaprated t dryness t affrd the catechl. General Prcedures fr the Preparatin f Quinnes.30 T a 100 ml rund bttm flask equipped with a Nz adapter and stir bar was added the t -Butyl-dihydrxybiphenyl ( mml), F6tizn's Reagent (AgZC03 n celite) ( g, excess), NaZS04 ( g, excess), distilled CHzClz(20mL), and purged 3 times with Nz. The reactin mixture was stirred fr ISh under Nz. Filtratin thrugh celite and cncentratin under reduced pressure affrds the quinnes. General Prcedure fr the Preparatin f Semiquinnes. T a 20mL vial equipped with a stir bar in an inert atmsphere was added the catechl (1 equivalent, mml), quinne (1 equivalent, mml),dry THF (-5mL) and stirredfr 5 min. Then,KH (-2mg, 0.50mml) was added and the reactin mixture stirred fr 30 min. The resulting suspensin was filtered t remve excess KH, and a O.lmM slutin f the semiquinne in THF prepared fr EPR studies. S3

4 2. NMR Spectra f Characterized Cmpunds. ~{ ~{ -, \ _ L r! ::r: w (J en , \ ' -'"' ::r: U'I ~ \ w ru '2 - S4 -

5 _ _17S.!1' _ _1"'.515 _151.13' _ _ _130.11', ' S5

6 $ (J ri- I _..r '""\ r r "'"\ S6 ----

7 '\,,= C' / \- <,.. r \L / CD _ a '-:>0 ::r::... 0 I b:i -= S7

8 .--- ~ CD J~ ~ 0"1 :{ ~ ~{ Ul ~ ) A :{ 1f w--l I '- \ " 3 N 11\_ / 0 z 3 IV 0... I OJ s:: ~{.I S8

9 { 1?=- CD ] ( I... t:jj c {r t2 j -[., CD C> " :{ I', r;-[ -...1_ r --J CD 01 --J ~ Ul w -- S9 ---

10 mi P, :{ :J '-- :""-{ w -...J -. I 70 'I :l\ 3 V-..3 I J J:>. { y -...J i-u '"C 3: w ru -0 rj7 ~ ~.t) 1:... SlO

11 :{CDl?-= :{ { :-{ ---.J I ---.J CD ---.J ,..' 01 ~{ t.n (] w I 7\J )I ,j;: Sll

12 , ' ' ,e r ~ S12

13 (» { \ : l :{ ", S r-7.&85 _7.U2 : {..., I I ;" cn-j I ~ ~ 7... I _ ;fj ~ \ _.,. S::'-.". w :{ :"" j ~ N '--7.U8 ~~~~~. :: \::7.222 U1 ~4.051 ~ \ N <II <:> CD { <II S

14 ;{ ~i..} ' J>. t ' ;.. f..~ ' ~ { {. ~ ~{ : { 'J... en t;~9~;o f:i..932 r ::::: '-7.929! en = ;., :r: :., w ] - c c: --== c c:::: N :1 ( c C J,- {.,- C I r S14

15 en Ul... <=> N en Ul Ul Ul A Ul S15

16 ::t (") ::t... J CD (j") (Jl (j") (Jl (Jl (Jl - 516

17 C» 0 { ::r: '" () { r { 0 '-I \ J_ r,.m \ () ::r: '" C') (J1 ~ ~7.28S......~ "\ \-'.'72 \.-? \.-'.310 C') _6,'" 6.!l50 (J1 (J1 U1 (J N U1 "" { "C "C

18 ~{" r \ : { F \ '.z ~{~JF \ en (') ::r:... CJ' N "C "C S

19 :x:: '" (") ' n it-,

20 Ī ::r: 0 { 1 r=- { N =.j;>. M- { \ j,,-.., (" _7.848 : _7.373 _7.440 :-1 r- N _1.25' ml I ; { 1 \ j j (" I _,.,so 6.'22 U1 _5.4'6 w N S20

21 :r: + en.697, ' S21

22 Gaussian 98W ********************************************* Gaussian 98: x86-win32-g98reva.9 19-Apr Aug-2006 ********************************************* Fr Optimizatin f all Mlecules #P ub3lyp/epr-ii pt density=current Fr Frequency calculatins f all Mlecules #P ub3lyp/epr-ii freq gem=checkpint S22

23 SQ 7 - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z S23

24 SQ 10 - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z S24

25 SQ 17 - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z S25

26 SQ 25a - Crdinates f ptimized structure Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z S26

27 SQ 25b - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z S27

28 SQ Ttal Energy (Hartrees) Number f Imaginary Vibratinal Frequencies 7 E(UB+HF-LYP) = H - NImag=0 V/T = S**2 = E(UB+HF-LYP) = H NImag=0 -V/T = S**2 = E(UB+HF-LYP) = H NImag=0 -V/T = S**2 = a E(UB+HF-LYP) = H NImag=0 -V/T = S**2 = b E(UB+HF-LYP) = H NImag=0 -V/T = S**2 = All ptimized structures have zer imaginary frequencies. S28

29 9,9-Dimethyl Flurene Quinne-Semiquinne (6F7) and N-Methyl Carbazle Quinne-Semiquinne (16F17) Cyclic Vltammagrams. a 6F7 16F Reductin Ptential (V) a. Ferrcene-ferrcenium cuple mitted fr clarity. Experimental parameters: Samples (6F7), (16F17): IP: -0.30V V1: -1.3V V2: +0.30V FP: -0.3V Standard (ferrcenefferrcenium): IP: -0.50V V1: -1.3V V2: +0.20V FP: -0.5V S29