NMR Studies on Interactions between Diperoxovanadate Complexes and 1-Methylimidazole

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1 Vol. 65, , ACTA CHIMICA SINICA No. 16, NMR N- a,b a a a *,a,b a *,b ( a ) ( b ), (0.15 mol/l NaCl ), ( 1 H, 13 C 51 V) (COSY) NMR [OV(O 2 ) 2 LL'] n [n 1 3, LL' oxalate ( oxa) picolinate( pic) bipyridine( bipy) 1,10-phenanthroline( phen), bpv(oxa), bpv(pic), bpv(bipy) bpv(phen)] N- ( ), 4 : bpv(oxa) bpv(pic) bpv(bipy) bpv(phen)., [OV(O 2 ) 2 ()],. ; N- ; ; NMR Studies on Interactions between Diperoxovanadate Complexes and 1-Methylimidazole YU, Xian-Yong a,b LI, Guo-Bin a ZHENG, Bai-Shu a HUANG, Hao-Wen a YI, Ping-Gui*,a,b PENG, Hong-Liang a CHEN, Zhong*,b ( a Hunan Province College Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan ) ( b State Key Laboratory for Physical Chemistry of Solid Surface, Xiamen University, Xiamen ) Abstract To understand the effects of organic ligands of the diperoxovanadate complexes on the reaction equilibrium, the interactions between a series of diperoxovanadate complexes [OV(O 2 ) 2 LL'] n [n 1 3; LL' oxalate, abbr. oxa; picolinate, abbr. pic; 2,2'-bipyridine, abbr. bipy; and 1,10-phenanthroline, abbr. phen. The corresponding peroxovanadate species abbreviate bpv(oxa), bpv(pic), bpv(bipy), and bpv(phen)] and 1-methylimidazole (abbr. ) in solution were explored using multinuclear ( 1 H, 13 C, and 51 V) magnetic resonance, COSY, and variable temperature NMR in 0.15 mol/l NaCl ionic medium for mimicking the physiological conditions. The experimental results indicated the activity order of these four complexes with 1-methylimidazole as follows: bpv(oxa) bpv(pic) bpv(bipy) bpv(phen). Both the coordinating capability and the steric effect of the organic ligands affect the reaction equilibrium. At the same time, a new six-coordinated peroxovanadate species [OV(O 2 ) 2 ()] is formed due to the competitive coordination. Keywords diperoxovanadate; 1-methylimidazole; interaction; NMR * yipinggui@sohu.com Received March 28, 2007; revised May 22, 2007; accepted June 25, (No. 2003CB716005) (No. 06JJ30004) (No. 06B028) ( ) (No. 3502Z ) (No. Wkj ) (No. E-55107).

2 No. 16 NMR N- 1549,, Cantley [1] ATP, Dubyak [2],, [3 4]., Orvig [5] 3 4 5, Abu-Omar [6] DNA, Crans [7],., (NMR) [8 15] (ESI-MS) [11 13,15] [16] [8 10,17]. Pettersson [18] 51 V NMR, α- ; Tracey [19,20] ; [8 15].,,., ( 1 H, 13 C 51 V) (COSY) NMR, [OV(O 2 ) 2 LL'] n (n 1 3, LL' ) N- ( ),. 1 Varian Unity 500 MHz. NMR : 25, NaCl (0.15 mol/l), 1 H 13 C NMR DSS, 51 V NMR VOCl 3. 1 H NMR : 4.0 s, 5.0 µs, 2.0 s, 10 khz. 13 C NMR : 2.0 s, 4.0 µs, 0.7 s, 50 khz, 5000, 2 Hz, 128 k. 51 V NMR : 5.0 µs, 100 khz, 0.5 s, 1.0 s, 128, 128 k, 10 Hz. NaOH, NH 4 VO 3, NaC 2 O 4, N-, 2,2'-, 1,10-30% H 2 O 2,,. [OV(O 2 ) 2 LL'] n, (Scheme 1) [n 1 3, LL' 2,2'- 1,10- oxa, pic, bipy phen, bpv(oxa), bpv(pic), bpv(bipy) bpv(phen), bpv ]. bpv(oxa), bpv(bipy) bpv(phen) NH 4 VO 3 /H 2 O 2 / ( 1 5 1), bpv(pic) NH 4 VO 3 /H 2 O 2 / /NaOH( ). Scheme bpv (L") 51 V 1 H NMR 1(a) NH 4 VO 3 /H 2 O 2 /oxa ( 1 5 1, 0.2 mol/l, ) 51 V NMR, δ , bpv(oxa) [OV(O 2 ) 2 (L"')] (L"' D 2 O HOD) [12,21],, bpv(oxa) [OV(O 2 ) 2 (L"')], δ 748 [ [OV(O 2 ) 2 ()], bpv()],, 1 2(b). δ 732, [V(O 2 ) 3 ] [12,19,20]. 1, bpv(oxa) [V(O 2 ) 3 ] 16%; 1.5, bpv(oxa) [V(O 2 ) 3 ].

3 1550 Vol. 65, 2007,. N- 1 H NMR, (bpv ) N-,, 3. 3(a), N- ( bpv(oxa), ), ; 3(b), (c) (d) N-,, : bpv : bpv(pic) bpv(bipy) bpv(phen)., 51 V NMR 1 bpv(oxa) 51 V NMR Figure 1 51 V NMR spectra of the interaction system between bpv(oxa) and (a) (e) corresponding to the molar ratio of (L")/bpV 0, 0.5, 1.0, 1.5, and 2.0, respectively. The bpv means both bpv(oxa) and [OV(O 2 ) 2 (L"')] (L"' D 2 O or HOD). The total concentration of vanadate species is 0.20 mol/l, bpv(pic) bpv(bipy) bpv(phen) (0.2 mol/l), 51 V δ 744, , 2(a). bpv(pic) bpv(phen),, δ 748, 2(b). bpv(bipy), 51 V NMR, 218 Hz 279 Hz, 50, 51 V NMR, 452 Hz, bpv(bipy) [OV(O 2 ) 2 ()],, bpv : bpv(oxa) bpv(pic) bpv(phen). : bpv(oxa) bpv(pic) bpv(bipy) bpv(phen)., N-,., bpv(phen) ( 1 1), bpv 5, bpv 1 H NMR Figure 3 The 1 H NMR spectra of the interaction systems between bpv and (L") The total concentration of vanadate species is 0.20 mol/l, respectively, 51 V NMR. 4 bpv(phen) (0.2 mol/l) bpv 51 V NMR Figure 2 The 51 V NMR spectra of the interaction systems between bpv and N-Me- Im (L") The total concentration of vanadate species is 0.20 mol/l, respectively V NMR, : (1),,, 10 bpv(phen) 2.7, [OV(O 2 ) 2 -

4 No. 16 NMR N ()] ,., bpv(phen) [OV(O 2 ) 2 ()] Hz Hz; (2), bpv(phen), [OV(O 2 ) 2 ()],, phen, [OV(O 2 ) 2 - ()], bpv(phen) 25 63% 55 57%; (3),, [OV(O 2 ) 2 ()], 4(d) (e),, [OV- (O 2 ) 2 ()]. phen ( 2.3 ), phen ( ), phen. 55,, [OV(O 2 ) 2 ()] ( ),, phen, [OV(O 2 ) 2 ()].,, [OV(O 2 ) 2 - ()]. 2.2 bpv 1 H 13 C NMR 1 4, :, ;,. bpv(oxa), oxa 1 H, 1 H NMR., 1 H 13 C NMR 4,, pic, bipy phen., bpv(pic), bpv(bipy) bpv(phen) 7 [ 51 V [OV(O 2 ) 2 (Py)] (Py, δ 712), N, ] [11],,, pic, bipy phen,, ;, oxa,, [12]. bpv(bipy) ( 1 1), 1 H, NMR. 5 1 H- 1 H COSY, a bipy, bipy V N [22],, COSY 6 ; b bipy; c 4 bpv(phen) 51 V NMR Figure 4 51 V NMR spectra of the interaction system between bpv(phen) and at different temperatures From bottom to top, the temperature increases, and then decreases 5 bpv(bipy) 1 H- 1 H COSY Figure 5 The 1 H- 1 H COSY spectrum of aromatic ring of the interaction systems of bpv(bipy) and (a) Coordinated bipy; (b) free bipy; (c) coordinated ; (d) free

5 1552 Vol. 65, 2007 Table 1 1 bpv 1 H 13 C NMR 1 H and 13 C NMR spectral data of the interaction systems of bpv and Systems Species Chemical shifts 1 H δ 13 C δ [OV(O 2 ) 2 (oxa)] 175.8, Oxa bpv(oxa)+ a [OV(O 2 ) 2 ()] 3.76 (s, 3H, CH 3 ), 7.23 (s,, 7.34 (s,, 8.11 (s, 141.6, 129.7, 125.0, (s, 3H, CH 3 ), 7.18 (s,, 7.23 (s,, 8.17 (s, 138.9, 129.7, 125.0, 37.1 bpv(pic)+ a bpv(bipy)+ a bpv(phen)+ b [OV(O 2 ) 2 (pic)] Pic [OV(O 2 ) 2 ()] 7.73 (s, 1H, Py-H), 8.01 (s, 1H, Py-H), 8.16 (s, 1H, Py-H), 9.27 (s, 1H, Py-H) 7.40 (s, 1H, Py-H), (m, 2H, Py-H), 8.45 (s, 1H, Py-H) 3.72 (s, 3H, CH 3 ), 7.20 (s,, 7.32 (s,, 8.09 (s, 3.63 (s, 3H, CH 3 ), 7.00 (s,, 7.06 (s,, 7.76 (s, 7.32 (s, 1H, Py-H), 7.60 ~ 7.65 (m, 1H, Py-H), (m, 1H, Py-H), 7.95 (d, J= 7.63 Hz, 1H, Py-H), (m, 1H, Py-H), [OV(O 2 ) 2 (bipy)] 8.19 (d, J= 7.63 Hz, 1H, Py-H), 8.41 (s, 1H, Py-H), 9.43 (s, 1H, Py-H) Bipy [OV(O 2 ) 2 ()] [OV(O 2 ) 2 (phen)] Phen [OV(O 2 ) 2 ()] (m, 2H, Py-H), (m, 4H, Py-H), (m, 2H, Py-H) 3.68 (s, 3H, CH 3 ), 7.16 (s,, 7.29 (s,, 8.06 (s, 3.57 (s, 3H, CH 3 ), 6.90 (s,, 6.98 (s,, 7.58 (s, 7.27 (d, J= 8.85 Hz, 1H, Phen-H), 7.32 (dd, J= 7.93, 4.27 Hz, 1H, Phen-H), 7.37 (d, J= 8.85 Hz, 1H, Phen-H), 7.62 (dd, J=8.24, 4.58 Hz, 1H, Phen-H), 7.75 (d, J= 7.93 Hz, 1H, Phen-H), (m, 1H, Phen-H), 8.68 (d, J=4.27 Hz, 1H, Phen-H), 9.59 (d, J=4.58, 1H, Phen-H) 7.04 (s, 2H, Phen-H), 7.49 (dd, J=7.93, 4.58 Hz, 2H, Phen-H), (m, 2H, Phen-H), 8.34 (d, J= 3.96 Hz, 2H, Phen-H) 3.59 (s, 3H, CH 3 ), 7.06 (s,, 7.24 (s,, 7.99 (s, 3.46 (s, 3H, CH 3 ), 6.80 (s,, 6.86 (s,, 7.42 (s, a bpv(oxa) bpv(pic) bpv(bipy) 1 1, b bpv(phen) , 155.1, 153.5, 144.6, 130.7, , 155.6, 150.9, 140.2, 128.4, , 129.8, 125.0, , 128.0, 124.3, , 156.1, 151.3, 148.6, 144.2, 141.6, 129.0, 128.3, 125.3, , 151.4, 140.7, 127.1, , 129.7, 124.9, , 129.2, 124.1, , 148.7, 146.2, 143.1, 142.6, 139.7, 131.7, 130.8, 129.3, 128.2, 127.3, , 146.3, 139.3, 130.7, 128.6, , 129.7, 124.8, , 129.7, 123.9, 35.6 d H C NMR, 5, 6, bpv(bipy) bpv [9,12,13,15,23] NMR, 2. bpv(oxa), bpv(pic) bpv(bipy),

6 No. 16 NMR N ), phen bipy., phen.,, oxa pic bipy phen bpv(bipy) 13 C Figure 6 13 C spectrum of the interaction system of bpv(bipy) and (a) Coordinated bipy; (b) free bipy; (c) coordinated ; (d) free : (1) [OV(O 2 ) 2 - (LL')], TS1, LL', LL', 6 [OV(O 2 ) 2 ()], (a) (b); (2) [OV(O 2 ) 2 ()] LL',, TS2, [OV(O 2 ) 2 (LL')], (c) (d). bpv(phen), phen, TS1, phen bpv(phen), bpv(phen), bpv(phen).,, bpv(oxa) 7 6 [12],, bpv(oxa). oxa, TS1. pic, N O, Pettersson [18],,, pic oxa bipy. bpv(pic) bpv(bipy),,. bipy phen,, phen bipy π, phen π, (bipy pic 2 bpv Scheme 2 The possible interaction modes between bpv(oxa), bpv(pic), bpv(bipy) or bpv(phen) and 3 NMR [OV(O 2 ) 2 LL'] n N-. N- 4 : bpv(oxa) bpv(pic) bpv(bipy) bpv(phen).. [OV(O 2 ) 2 - ()],. References 1 Cantley, L. C. Jr.; Resh, M. D.; Guidotti, G. Nature 1978, 272, Dubyak, G. R.; Kleinzeller, A. J. Biol. Chem. 1980, 255, Thompson, K. H.; Orvig, C. Science 2003, 300, Crans, D. C.; Smee, J. J.; Gaidamauskas, E.; Yang, L. Q. Chem. Rev. 2004, 104, Thompson, K. H.; Orvig, C. Coord. Chem. Rev. 2001, 219, Sam, M.; Hwang, J. H.; Chanfreau, G.; Abu-Omar, M. M. Inorg. Chem. 2004, 43, 8447.

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