5654
J . Am. Chem. SOC.1992, 114, 5654-5664
identified,’I the present study is the first demonstration of this phenomenon for platinated duplex DNA. This assignment was made by means of a careful analysis of platinum stereochemistry with the aid of ISN NMR spectroscopy. In addition, modification of the amine ligands in the platinum coordination sphere has been shown to influence the selectivity for d(ApG) and d(GNG) intrastrand cross-link formation. The observed reduction in the number of d(ApG) cross-links suggests the exciting possibility that the mutagenic activity of compounds 1 and 2 may be decreased relative to cisplatin. The selective formation of the two d(GpG)-2 orientational isomers, corresponding to the 3’ versus 5’ orientation of the cyclohexylamine ligand, has been shown to play a small but measurable role in the processing of DNA platinated with complex 2. In particular, both isomers are slightly less efficient than cisplatin in blocking replication despite the increased bulk of the platinum lesion, and each terminates DNA synthesis to different degrees at the two observed sites. The availability of high-resolution X-ray structural studies of cisplatin and related
complexes bound to duplex DNA will help in the understanding of the hydrogen bonding or steric factors that are responsible for these differences and should provide a basis for analyzing the relationship between the structures of specific platinum-DNA adducts and their processing by cellular components. Studies toward this end are in progress, from which may ultimately arise a rational basis for platinum antitumor drug design. Acknowledgment. This work was supported by a grant from the National Cancer Institute of the National Institutes of Health (CA 34992). J.F.H. thanks the American Cancer Society for a postdoctoral fellowship. We are grateful to Drs. C. M. Giandomenico and M. J. Abrams a t Johnson Matthey Biomedical Research for preprints and cisplatin, to the Stable Isotopes Laboratory at Los Alamos National Laboratory for providing 1sN7-2’-deoxyguanosine, to Dr. C. E. Costello at MIT for FAB(MS/MS) spectra, and to Dr. K. M. Comess for helpful discussions.
(71) Alink, M.; Nakahara, H.; Hirano, T.; Inagaki, K.; Nakanishi, M.; Kidani, Y.; Reedijk, J. Inorg. Chem. 1991, 30, 1236.
SupplementaryMaterial Available: Figure S1, displaying the FAB (MS/MS) spectrum of the d(ApG)-2 adduct (1 page). Ordering information is given on any current masthead page.
Dihydrogen Complexes of Metalloporphyrins: Characterization and Catalytic Hydrogen Oxidation Activity James P. Collman,*9tPaul S. Wagenknecht,+James E. Hutchison,+Nathan S. Lewis,+?$ Michel Angel Lopez,+Roger Guilard,t*% Maurice L’Her,+JAksel A. Bother-By,l and P. K. Mishral Contribution from the Departments of Chemistry, Stanford University, Stanford, California 94305, and Carnegie Mellon University, Pittsburgh, Pennsylvania 1521 3. Received October 21, 1991
Abstract: A series of monometallic dihydrogen complexes of the type M(OEP)(L)(H2) (M = Ru, Os; L = THF, *Im) was synthesized and characterized by IH NMR. The H-H bond length was found to increase when Os was replaced by Ru or when *Im was replaced by THF. The bond distances (as determined by TI) range from 0.92 to 1.18 A. The first example of a bimetallic bridging dihydrogen complex, Ru2(DPB)(*1m),(H2),was also prepared. The H2 ligand is simultaneously bound to both Ru-metal centers. High-field ‘H NMR experiments (620 MHz) revealed a -7.37 Hz dipolar splitting of the H2 ligand for this complex. Analysis of this splitting suggests that the H2 ligand is bound with the H-H axis perpendicular to the Ru-Ru axis. These complexes were examined as possible catalysts for the oxidation of dihydrogen through prior heterolytic activation of H2. Only Ru(OEP)(THF)(H2) can be conveniently deprotonated. Ru(OEP)(THF)(H2) is also implicated in the Ru(OEP)(THF), catalyzed isotopic exchange between H2 and D 2 0 in THF solution. Each step for this mechanism has been elucidated. We have also achieved catalytic dihydrogen oxidation using [Ru(OEP)I2 adsorbed onto graphite. Two mechanisms for this ruthenium porphyrin catalyzed dihydrogen oxidation are presented and compared.
Though thermodynamically unstable in an oxygen atmosphere, dihydrogen is kinetically inert and is not reactive unless activated with a suitable catalyst. Such catalysis occurs naturally in certain microorganisms that have been known since the turn of the century to consume dihydrogen.’ In 1931, Stephenson and Strickland2 proposed the first description of this phenomenon in terms of enzymatic activation of hydrogen and named the relevant enzymes hydrogenases. The physiological role of hydrogenases is to mediate the production and consumption of dihydrogen in the presence of cofactors such as nicotinamide adenine dinucleotide, cytochrome c3,and f e r r e d o ~ i n . ~However, .~ an important criterion for hyd‘Stanford University. ‘Present address: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91 125. ‘Present address: Universite de Bourgogne, Laboratorie de Synthese et d’Electrosynthbe Organom6tallique Associ6 au CNRS (UA 33), Facult6 des Sciences “Gabriel”, 21 100 Dijon Cedex, France. fl Present address: U.R.A. C.N.R.S. 322, Facult6 des Sciences, Universite de Bretagne Occidentale, 6 Avenue V. Le Gorgeu, 29287 Brat Cedex, France. ICarnegie Mellon University.
rogenase activity is the physiologically unimportant exchange of H2 and D 2 0 first characterized by Farkas in 1934 (eq l).536 H2 + D20 * D2 + H D + HDO H20 (1) Several authors3*’ have suggested that this activity indicates
+
(1) (a) Pakes, W. C. C.; Jollyman, W. H. J. Chem. SOC. 1901, 79, 386-391. (b) Harden, A. J . Chem. SOC.1901, 79, 601-628. (2) Stephenson, M.; Strickland, L. H. Biochem. J . 1931, 25, 205-214. (3) Holm, R. H. In Biological Aspects of Inorganic Chemistry; Addison, A. W., Cullen, W. R., Dolphin, D., James, B. R., Eds.; Wiley: New York, 1977; pp 71-112. (4) Schlegel, H. G.; Schneider, K. In Hydrogenases: Their Catalytic Activity, Structure and Function; Schlegel, H. G., Schneider, K., Eds.; Verlag-Erich Goltze KG: Gottingen, 1978; pp 15-44. (5) Farkas, A,; Farkas, L.; Yudkin, J. Proc. R. Soc. bndon A 1934, B I I S , 373. (6) Several authors have now reported this exchange. (a) Lespinat, P. A.; Berlier, Y.; Fauque, G.; Czechowski, M.; Dimon, B.; LeGall, J. Biochimie 1986,68, 55-61. (b) Arp, D. J.; Burris, R. H. Biochim. Biophys. Acra 1982, 700, 7-15. (c) Teixeira, M.; Fauque, G.; Moura, I.; Lespinat, P. A.; Berlier, Y.; Prickril, B.; Peck, H. D., Jr.; Xavier, A. V.; LeGall, J.; Moura, J. J. G. Eur. J . Biochem. 1987, 167, 47-58 and references therein.
0002-7863192115 14-5654$03.00/0 0 1992 American Chemical Society
Dihydrogen Complexes of Metalloporphyrins
J. Am. Chem. SOC.,Vol. 114, No. 14, 1992 5655
heterolytic activation of dihydrogen. In fact, in 1954 Krasna and Rittenberg' first proposed that many of the functions of hydrogenase enzymes proceed through heterolytic activation of dihydrogen to form an active hydride (eq 2). The isotopic exchange
H2 + E = EH-
+ H+
(2) between H2 and D 2 0 is then explained in terms of heterolytic hydrogen activation, followed by proton exchange. Functional hydrogenase enzyme models which catalyze the isotopic exchange process in eq 1 and which catalyze substrate reduction using dihydrogen have been published by H a l p e d and Henri~i-OlivE.~ The recent discovery of dihydrogen complexes has sparked interest in their possible intermediacy in dihydrogen activation.I0 The high acidities of some metal bound dihydrogen ligands" imply their possible intermediacy in the heterolytic activation of dihydrogen. Such reactivity led Crabtree to propose the intermediacy of metal bound dihydrogen and hydrides in hydrogenase enzyme reactivity.I2 More recently Albeniz et al.I3 reported several dihydrogen complexes which catalyze the exchange given in eq 1. Additionally, Zimmer et al.I4 reported a Ni-S complex, which more closely resembles the structure of hydrogenase enzymes, that also catalyzes this exchange. Figure 1. Proposed structure of Ru~(DPB)(*I~)~(H~). We previously reported1s*16 that metalloporphyrin hydrides and dihydrogen complexes can perform many of the same functions (M = Ru, Os; L = *Im, THF) with benzoic acid a t -78 OC in as hydrogenase enzymes: H 2 / D 2 0exchange, dihydrogen actiTHF-d8 solvent (eq 3). Decomposition of the resulting H2 vation, and nicotinamide reduction. Because the mechanisms of this reactivity are more easily studied with these discreet metalloporphyrins than with large protein enzymes, we sought to extend our study of metalloporphyrin dihydrogen complexes presuming that their reactions may give insight into hydrogenase reactivity . complexes was followed by 'H NMR while raising the temperature Herein, we describe the preparation of several new dihydrogen and collecting a spectrum every 10 'C. Upon warming, the complexes of metalloporphyrins, including the first example of dihydrogen complexes decompose by replacement of H2with THF a complex in which dihydrogen bridges two metal centers. Data from our previously characterized dihydrogen c o m p l e x e ~are~ ~ ~ ~ to ~ form the corresponding M(OEP)(L)(THF) (eq 4). Significant included here for completeness and comparison. The reactivity of these dihydrogen complexes is examined, with special attention given to the deprotonation of the dihydrogen ligand as a possible means of dihydrogen activation. We have also demonstrated catalytic dihydrogen oxidation, near the thermodynamic potential, decomposition of the dihydrogen complexes Os(OEP)(*Im)(H2) with an electrode treated with a metalloporphyrin. Evidence is and Ru(OEP)(THF)(H2) occurred at -20 and -30 OC, respecpresented for the intermediacy of a dihydrogen complex in this tively. Attempts to synthesize Ru(OEP)(*Im)(H2) by protonation process as well as in the metalloporphyrin catalyzed exchange of the K[Ru(OEP)(*Im)(H)] with benzoic acid in THF-d8were between H2 and D20. unsuccessful. The product from this reaction was Ru(0EP)Results (*Im)(THF),I6 consistent with protonation of the metal hydride Syntaesi of the Dihydrogen Complexes M(OEP)(L)(H,). The followed by rapid loss of dihydrogen. Similar attempts in tolumonomeric dihydrogen complexes Ru(OEP)(THF)(H2) and ene-de resulted in no bound dihydrogen. Os(OEP)(THF)(H2) O S ( O E P ) ( * I ~ ) ( Hwere ~ ) ~ prepared ~ by protonation of the corwas synthesized by protonation of the K[ Os(0EP) (THF) (H)] responding metalloporphyrin hydride anions16K[M(OEP)(L)(H)] in THF-d8at room temperat~re.'~ This complex decomposes over the course of 1 day to form Os(OEP)(THF),. In THF-d8, the THF ligand on all of the above complexes is not observed in the (7) Krasna, A. I.; Rittenberg, D. J. Am. Chem. Soc. 1954, 76,3015-3020. 'H N M R spectrum due to exchange with THF-d8. However, (8) (a) Halpern, J.; James, B. Can. J . Chem. 1966, 44, 671-675. (b) Harrod, J. F.; Ciccone, S.; Halpern, J. Can. J . Chem. 1961, 39, 1372-1376. Os(OEP)(THF)(H2) has also been synthesized by protonation (9) Henrici-Olivt, G.; Olivt, S. J . Mol. Cataf. 1976, I, 121-135. of K[Os(OEP)(THF)(H)] in toluene-d8 at -78 "C; in this case (10) Kubas, G. J. Acc. Chem. Res. 1988, 21, 120-128. the trans THF ligand was detected by 'H N M R spectroscopy. (11) (a) Chinn, M. S.; Heinekey, D. M.; Payne, N. G.; Sofield, C. D. All of the dihydrogen complexes display sharp diamagnetic 'H Orgunomefaffics1989,8, 1824-1826. (b) Jia, G.; Morns, R. H. Inorg. Chem. 1990,29, 581-582. (c) Jia, G.; Moms, R. H.; Schweitzer, C. T. Inorg. Chem. N M R resonances, with the methylene protons of the OEP ethyl 1991,30,593-594. (d) Jia, G.; Morris, R. H. J . Am. Chem. Soc. 1991,113, substituents appearing as a multiplet, indicating that the two faces 875-883. (e) Crabtree, R. H.; Lavin, M.; Bonneviot. L. J . Am. Chem. SOC. of the porphyrin are inequivalent. This precludes the assignment 1986,108,4032-4037. (f) Chinn, M. S.; Heinekey, D. M. J . Am. Chem. Soc. of these resonances to trans dihydrides. 1987,109, 5865-5867. (g) Chinn, M. S.; Heinekey, D. M. J . Am. Chem. Soc. 1990, 112, 5166-5175. Synthesis of the Bridged Dihydrogen Complex. Addition of 2 (12) Crabtree, R. H. Inorg. Chim. Acfa 1986, 125, L7-L8. equiv of 1-tert-butyl-5-phenylimidazole(*Im) to a hydrogen(13) Albeniz, A. C.; Heinekey, D. M.; Crabtree, R. H. Inorg. Chem. 1991, saturated benzene solution of the cofacial metalloporphyrin dimer, 30, 3632-3635. (14) Zimmer, M.; Schulte, G.; Luo,X.-L.; Crabtree, R. H. Angew. Chem., Ru2(DPB), results in the immediate formation of Ru2(DPB)Int. Ed. Engl. 1991, 30, 193-194. (*Im)2(H2)(eq 5 and Figure 1). The IH N M R data supporting (15) Collman, J. P.; Wagenknecht, P. S.; Hembre, R. T.; Lewis, N. S. J . Am. Chem. Soc. 1990, 112. 1294-1295.
(16) Following paper in this issue. (17) Collman, J. P.; Hutchison, J. E.; Wagenknecht, P. S.; Lopez, M. A,; Guilard, R.; Lewis, N. S. J. Am. Chem. SOC.1990, 112, 8206-8207. (18) Abbreviations: OEP = octaethylporphyrinato dianion; DPB = diporphyrinatwbiphenylene tetraanion; THF = tetrahydrofuran; 'Im = 1fer(-butyl-5-phenylimidazole; PPh3 = triphenylphosphine.
*Im
5656 J. Am. Chem. SOC.,Vol. 114, No. 14, 1992
Collman et al.
Table I. Temperature Dependence of the Relaxation Rates of the Dihydrogen Ligands, Performed a t 400 M H z
T ("C) -7 5
Ru(0EP)(TW(H2)"
28 27 26 25c
0
dec
50
"In THF-d8.
Os(0EP)- Ru,(DPB) (*~m)(H2)" (*W2(H2Ib 73
-70 -60 -50 -45 -40 -30 -20 -10 10 20 30
Os(0EP)(THF)(H2)"
44 35 31
130 122
50
44 1 390
39 112 111 107 112 120 124 130
28'
dec
288 240 217 159 144 134 133 180
dec toluene-d8. 'Measured on weak signals.
this formulation have previously been published." Under 1 atm of H2 approximately 5% of the diporphyrin exists as a complex with no internal ligand, suggesting that the bridging dihydrogen complex is in equilibrium with the bis 5-coordinate species, R u ~ ( D P B ) ( * I (eq ~ ) ~6 ) . This bis 5-coordinate species can ir-
0.003
0.005
0.004
l/r ( O K - ' ) Figure 2. Plot of the In ( T I )(Ti measured in ms) vs reciprocal temperature (temperature measured in K) for the complexes Os(0EP)(THF)(H,) in THF-d, ( 0 )and R U ~ ( D P B ) ( * I ~ ) ~in( H toluene-d8 ~) (+.) a t 400 MHz. Note: Near the minimum, a simple linear relationship is not expected because the relaxation rate is not a linear function of either rC or rC-l as the conditions >> 1 or w2r,2 9OS~(DPB),~O Fe2(DPB),51and R u ~ ( D P B ) ( P P ~l-tert-butyl-5-phenylimidazole, *Im;52and R U ( O E P ) ( T H F ) ~were ' ~ ~ prepared ~~ according to the literature procedures. Hydrogen (99.999%) and deuterium (99.9%) were used as received from Liquid Carbonic. Hydrogen-deuteride gas was used as prepared by dropping D20onto a slurry of sodium hydride in benzene and passing the gas through a pipet packed E ~ , ~ ( vNHE) s = 0.000 V - 0.059 (pH) V (17) with activated alumina. The HD flow was controlled by controlling the D20 addition rate. The isotopic purity was >80% as determined by gas At p H = 13, the thermodynamic potential for H2 oxidation is chromatography. -0.77 V, whereas we find the half-wave potential for the catalyzed All manipulations of the metalloporphyrin hydrides and dihydrogen hydrogen oxidation occurs at -0.62V. Thus, our system operates complexes were performed in a Vacuum/Atmospheres Co. inert atmowith a 0.15-V overpotential. Because there is an overpotential sphere dry box equipped with an HE493 Dri-Train and operated under for hydrogen oxidation using this catalytic system, it is thermoan argon atmosphere. Oxygen levels ( 1 5 ppm) were monitored by a dynamically impossible to reduce protons using the microscopic Vacuum/Atmospheres Co. A0316-C trace oxygen analyzer. Solvent manipulations and degassing of air-sensitive samples were performed on reverse of the above hydrogen oxidation mechanism. Performing a bench top vacuum line in Schlenk flasks and NMR tubes fitted with such a process would mean operating at a 0.15-V"underpotential". J. Young Teflon valves and O-ring vacuum adapter fittings. 'H NMR Consequently, to find a catalyst for proton reduction, the operating data were recorded on Varian XL-400 and GEM-200 instruments. potential of the catalyst must be changed by altering the central High-field 'H NMR experiments were recorded on the 620-MHz inmetal or ancillary ligands. strument at Carnegie Mellon University. All electrochemical experiThe more hydridic bridged complex R U ~ ( D P B ) ( * I ~ ) ~ ( H ~ments ) employed a Princeton Applied Research 175 wave generator, and displays no catalytic activity for hydrogen oxidation. At pH = the 173 Potentiostat/Galvanostat. All electrochemicalexperiments in 13,no significant deprotonation of the bridging dihydrogen ligand nonaqueous solution were performed in the inert atmosphere box. The occurs; our solution studies with various bases suggest its pK, to working electrode (platinum disk, r = 0.5 mm) was circumscribed by the platinum wire loop auxiliary electrode in a 2-mL compartment separated be >20. The acidity of the dihydrogen ligand could in principle from the reference electrode by a luggin capillary. The reference elecbe increased by oxidation; however, such oxidation appears to trode was a Ag wire that was referenced to ferrocene at the conclusion destroy the affinity of the bimetallic site for dihydrogen. Such of the experiment. Water for aqueous electrochemical experiments was a dilemma illustrates the delicate balance of these mechanisms. purified to 18 MQ cm using a Barnstead Nanopure I1 water filter. ElectrochemicalStudies on Graphite. Electrochemical studies of meConclusions talloporphyrins adsorbed onto edgeplane graphite electrodes were perWe have shown that metalloporphyrins of various electronic formed outside the drybox in a 9-cm-diameter flat-bottom cell fitted with and steric constitution are capable of binding dihydrogen. The three joints, one each for the graphite working electrode, gold auxiliary use of the porphyrin ligand has greatly simplified the synthesis electrode, and saturated calomel reference electrode. A syringe needle was inserted through a Teflon stopcock to purge with argon and hydrogen and characterization of these dihydrogen complexes because of gas. The cell was filled to a depth of 3 cm with the backing electrolyte the lack of readily accessible cis-coordination sites, the absence of ligand protons near enough to affect the dipolar relaxation of the dihydrogen ligand, and the ease with which we were able to (48) Yang, E. S.;Chan, M.-S.; Wahl, A. C. J . Phys. Chem. 1975, 79, modify the trans ligand. Ru(OEP)(THF)(H,) is especially in2049-205 2. teresting because deprotonation of this complex readily occurs (49) Collman, J. P.; Kim, K.; Leidner, C. R. Inorg. Chem. 1987, 26, 1152-1157. to form an active hydride which is capable of reducing pyridinium (50) Collman, J. P.; Garner, J. M. J . Am. Chem. SOC.1990,112, 166-173. salts and one-electron oxidants.I6 These factors, coupled with its (51) Collman, J. P.; Wagenknecht, P. S. Unpublished. capacity for catalyzing the H2-D20 exchange reaction, suggest (52) vanleusen, A. M.; Schaart, F. J.; vanleusen, D. Rec. J . R . Neth. that this complex is a reasonable model for the non-porphyrinic Chem. SOC.1979, 98, 258-262. ( 5 3 ) Venburg, G. D. Ph.D. Dissertation, Stanford University, 1990. hydrogenase reactivity. The intermediacy of the [Ru(OEP)-
5664 J. Am. Chem. Soc., Vol. 114, No. 14, 1992 solution of the appropriate pH and purged for 30 min with argon. A 7.5-mm-diameter edgeplane graphite electrode was admitted into the drybox and immersed in a to lo4 M solution of [Ru(OEP)I2 in benzene for 2-3 min to adsorb the porphyrin onto the surface.54 The electrode was removed from the solution and allowed to dry in the drybox atmosphere. The electrode was removed from the drybox in a Schlenk flask under Ar, removed from the flask and quickly attached to a Pine instruments ASR2 rotator and admitted to the argon purged solution. Cyclic voltammetry and a slow scan (5 mV/s) rotating disk experiment were performed under the Ar atmosphere. The solution was subsequently purged for 15 min with hydrogen and the experiments repeated. The experiments were then repeated under Ar then H2 using the same electrode. Identical experiments were performed by adsorbing benzene solutions of Ru,(DPB) and Ru,(DPB)(*Im),(H,) onto the graphite surface. The potentials were corrected for the potential of SCE vs NHE. In Situ Preparation of the Dihydrogen Complexes. (a) Os(0EP)(THF)(H,). K[Os(OEP)(THF)(H)], 5 pmol in 1 mL of THF-d,, was treated with excess benzoic acid, -2 equiv. The dihydrogen complex was formed in 30% yield with the contaminants identified as [Os(OEP)], and Os(OEP)(THF),. The dihydrogen complex was characterized by 'H N M R spectroscopy, including Tivalues for the dihydrogen ligand and JHDvalues for the HD isotopomer (see text). 'H NMR (THF-d8, 20 OC, ppm): porphyrinic resonances, H,, 9.29 (s, 4 H), CH2 3.83 (m, 16 H), CH3 1.81 (t, 24 H); Os(H2) -30.00 (br s). (b) Ru(OEP)(THF)(Hz). An N M R tube attached to a rotationally balanced J. Young Teflon valve was obtained from R. J. Brunfeldt Co. Slightly below the point at which the valve seats, 13 pL of a toluene solution containing benzoic acid (50 mg of PhCOOH/1000 pL) was deposited and dried under reduced pressure, being careful to keep the 5 pmol of PhCOOH residue near the top of the tube. A THF-d, solution of K[Ru(OEP)(THF)(H)], 5 pmol, was carefully transferred to the bottom of the tube without disturbing the PhCOOH residue. The valve was seated and the sealed tube brought out of the inert atmosphere box and immediately submerged in a dry ice/acetone bath. After being cooled, the sample was shaken to ensure complete mixing of the hydride with the benzoic acid, at which time the sample changed colors from orange to red. The cooled sample was inserted into the N M R probe which had already been cooled and shimmed on a THF-d8 sample at -70 OC. The dihydrogen complex was contaminated with -15% Ru(OEP)(THF),. The dihydrogen complex was characterized by 'H N M R spectroscopy, including TI values for the dihydrogen ligand and JHD values for the H D isotopomer (see text). IH N M R (THF-d8, -60 OC, ppm): porphyrinic resonances, H,, 9.73 (s, 4 H), CH2 4.04 (m, 8 H), 3.91 (m, 8 H), CH3 1.87 (t, 24 H); Ru(H2) -30.91 (br s). (c) Os(0EP) (*Im) (H2). K [Os(0EP) (*Im) (H)] was protonated at low temperature, analogous to the synthesis for Ru(OEP)(THF)(H,). The dihydrogen complex was contaminated with 15% Os(0EP)(*Im)(THF). The dihydrogen complex was characterized by IH N M R
~~~~
(54) (a) Collman, J. P.; Hendricks, N. H.; Leidner, C. R.; Ngameni, E.; L'Her, M. Inorg. Chem. 1988, 27, 387-393. (b) Collman, J. P.; Denisevich, P.; Konai, Y.; Marrocco, M.; Koval, C.; Anson, F. C. J . Am. Chem. SOC.1980, 102, 6027-6036.
Collman et al. spectroscopy, including T , values for the dihydrogen ligand and JHD values for the H D isotopomer (see text). 'H N M R (THF-d8, -60 OC, ppm): porphyrinic resonances, H, 9.01 (s, 4 H), CH2 3.78 (m, 16 H), CH3 1.76 (t, obscured); Os(H2) -28.26 (br s); imidazole resonances, p-pheny16.98 (t. 1 H); m-phenyl 6.82 (t, 2 H); o-phenyl 5.98 (d, 2 H); Himidnrolc 1.36 (s, 1 H), 0.92 (s, 1 H); rerr-butyl 0.15 (s, 9 H). (d) R U ~ ( D P B ) ( * I ~ ) ~ ( Under H ~ ) . an argon atmosphere, a solution of Ru2DPB, 0.7 pmol, in benzene-d, or toluene-d8 (0.5 mL of a 1.4 mM stock solution) was bubbled for 5 min with hydrogen. Two equivalents of 1-tert-butyl-5-phenylimidazole(*Im; 58 pL of a 26.5 mM stock solution in benzene-d,) was added and hydrogen bubbling was continued for 2 min. 'H N M R (C6D6,ppm): porphyrinic resonances, H,, 8.81 (s, 2 H), 8.72 (s, 4 H); biphenylene 7.15 (2 H, obscured by residual solvent peak), 7.06 (d, 2 H), 6.85 (t, 2 H); C H 2 C H 34.38 (m, 8 H), 3.91 (m, 8 H); C H 3 3.50 (s, 12 H), 3.25 (s, 12 H); C H 2 C H 31.81 (t, 12 H), 1.61 (t, 12 H). Imidazole resonances, p-phenyl 6.21 (t, 2 H); m-phenyl 5.99 (t, 4 H); o-phenyl 4.38 (d, 4 H); Himidnrols -0.34 (s, 2 H), -0.40 (s, 2 H); tert-butyl -0.86 (s, 18 H); Ru-H2 -38.6 (bs, 2 H). Attempted Syntbesi of Ru(OEP)(*Im)(H2). K[Ru(OEP)(*Im)(H)] was protonated in THF-d, at -78 OC analogously to the preparation of Ru(OEP)(THF)(H2). Only Ru(OEP)(THF)(*Im) was observed as the product. The low-temperature protonation was also performed in toluene& Only Ru(OEP)(*Im) was observed as the product. bngitudinnl Relaxation Times, TI. Relaxation times were measured on a Varian XL-400 using the inversion recovery method. The XL-400 software computes a TI by assuming peak height is related to peak intensity by a single constant for all delay times and fitting peak height versus delay time to the equation describing Ti.We also calculated T i values for two cases by printing the dihydrogen resonances for a series of delay times and integrating by cutting and weighing the peaks. When these values were fitted to the T I equation, good agreement (112%) with the computer-calculated TI values was obtained. Hz/DzO Exchange. In the inert atmosphere box under argon, five 1-dram vials were charged with 0.5 mL of THF, 5 pmol of Ru(0EP)(THF)2, and a stir bar and sealed with a Teflon cap fitted with a valve through which a syringe needle could be inserted to sample the headspace. Two solutions containing 60 pmol KOD in 50 pL of D 2 0 (2800 pmol) and two containing 600 pmol KOD in 50 pL of D 2 0 were prepared and added to the vials. To the remaining vial, 50 pL of D 2 0 was added. Each vial was injected with 0.5 mL of H2 gas. The vials were taken from the inert atmosphere box and stirred vigorously at 50 O C for 160 min. Headspace samples from each vial were analyzed for H2, HD, and D2 gas using gas chromatography.'6 Isotope ratios for each of the identical runs were averaged.
Acknowledgment. We thank Dr. Robert Hembre for helpful discussions. We thank the National Science Foundation, National Institutes of Health, and the Gas Research Institute for financial support. The 620-MHz NMR spectra were obtained at the NMR Facility for Biomedical Studies, supported by the National Institutes of Health Grant RR00292. This is contribution No. 8521 from the Division of Chemistry and Chemical Engineering, California Institute of Technology.
