2007 65 Vol. 65, 2007 16, 1548 1554 ACTA CHIMICA SINICA No. 16, 1548 1554 NMR N- a,b a a a *,a,b a *,b ( a 411201) ( b 361005), (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 411201) ( b State Key Laboratory for Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005) 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 * E-mail: yipinggui@sohu.com Received March 28, 2007; revised May 22, 2007; accepted June 25, 2007. 973 (No. 2003CB716005) (No. 06JJ30004) (No. 06B028) ( ) (No. 3502Z20051027) (No. Wkj2005-2-019) (No. E-55107).
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( 1 5 1 1). Scheme 1 2 2.1 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 738 692, 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 ].
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, 747 742, 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, 0.01 0.08. 3 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) 1 5 2 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 25 55 51 V NMR, : (1),,, 10 bpv(phen) 2.7, [OV(O 2 ) 2 -
No. 16 NMR N- 1551 ()] 2.0. 55,., bpv(phen) [OV(O 2 ) 2 ()] 25 430 175 Hz 55 238 120 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
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, 170.4 Oxa 175.8 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, 36.8 3.76 (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), 7.76 7.84 (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), 7.74 7.82 (m, 1H, Py-H), 7.95 (d, J= 7.63 Hz, 1H, Py-H), 8.06 8.11 (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 ()] 7.22 7.27 (m, 2H, Py-H), 7.74 7.82 (m, 4H, Py-H), 7.99 8.04 (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), 8.06 8.12 (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), 8.06 8.12 (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) 1 5. 171.7, 155.1, 153.5, 144.6, 130.7, 128.0 175.7, 155.6, 150.9, 140.2, 128.4, 126.3 141.5, 129.8, 125.0, 36.8 140.7, 128.0, 124.3, 36.2 157.0, 156.1, 151.3, 148.6, 144.2, 141.6, 129.0, 128.3, 125.3, 123.5 157.3, 151.4, 140.7, 127.1, 124.7 141.5, 129.7, 124.9, 36.7 141.0, 129.2, 124.1, 35.8 156.5, 148.7, 146.2, 143.1, 142.6, 139.7, 131.7, 130.8, 129.3, 128.2, 127.3, 127.2 151.9, 146.3, 139.3, 130.7, 128.6, 125.9 141.4, 129.7, 124.8, 36.6 140.8, 129.7, 123.9, 35.6 d H. 6 13 C NMR, 5, 6, bpv(bipy) 4. 2.3 bpv [9,12,13,15,23] NMR, 2. bpv(oxa), bpv(pic) bpv(bipy),
No. 16 NMR N- 1553 ), phen bipy., phen.,, oxa pic bipy phen. 4. 6 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, 552. 2 Dubyak, G. R.; Kleinzeller, A. J. Biol. Chem. 1980, 255, 5306. 3 Thompson, K. H.; Orvig, C. Science 2003, 300, 936. 4 Crans, D. C.; Smee, J. J.; Gaidamauskas, E.; Yang, L. Q. Chem. Rev. 2004, 104, 849. 5 Thompson, K. H.; Orvig, C. Coord. Chem. Rev. 2001, 219, 1033. 6 Sam, M.; Hwang, J. H.; Chanfreau, G.; Abu-Omar, M. M. Inorg. Chem. 2004, 43, 8447.
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