2002 60 4, 687 691 ACTA CHIMICA SINICA Vol 60, 2002 No 4, 687 691 4 2PhC 4 Ph) MCp 2 ] ( M = Ti, Zr) Ξ ( 710069) Choukroun, Robert Valade, Lydie Cassoux, Patrick ( 31077),[ Cp 2 Ti (C CPh) 2 ] [ Cp 2 Zr (C CPh) 2 ], 4 2PhC 4 Ph) MCp 2 ] 1 (M = Ti), 2 (M = Zr),, 2 PhC 4 Ph Cp 2 V, Cp 2 Zr,,,,, Novel Heterometallic Complexes [ Cp 2 V( 2 4 2butadiyne) MCp 2 ] ( M = Ti, Zr) ZHAO, Jian2She 3 GU, Ai2Ping HE, Shui2Yang ( Shaanxi Key Laboratory of Physico2Inorganic Chemistry, Department of Chemistry, Northwest University, Xi an 710069) CHOUKROUN, Robert VALADE, Lydie CASSOUX, Patrick ( Laboratory of Coordination Chemistry, CNRS, F231077, Toulouse, France) Abstract The reaction of [ Cp 2 Ti (C CPh) 2 ], [ Cp 2 Zr (C CPh) 2 ] with vanadocene in toluene at room temperature gives heterodimetallic complexes [ Cp 2 V ( 2 4 2butadiyne) MCp 2 ] 1 (M = Ti), 2 (M = Zr), respectively These compounds, which have been characterized by elemental analysis, mass spectrometry, IR and Raman spectroscopy, exhibit similar magnetic susceptibilities According to an X2ray diffraction analysis of 2, the Cp 2 V and Cp 2 Zr metallocene moieties are bonded to a butadiene (or butadiyne) framework via the two internal carbon atoms for Cp 2 V, and via both the two internal carbon atoms and the two external carbon atoms for Cp 2 Zr The distances and angles observed around the internal carbon atoms of the butadiene framework indicate that both internal carbon atoms of butadiene skeleton are planar and tetracoordinated Keywords heterometallic complexes, structure elucidation, titanium, zirconium, vanadium Ti2V, MOCVD (MOCVD), TiVCN, Fisher gallane Ni2In Co2Ga [1 ], Ξ E2mail :Jszhao @nwu edu cn Received August 25,2001 ; revised October 19, 2001 ; accepted November 30,2001 (No 20071027), (No 00J K130)
688 Vol 60, 2002 [2 ], 130 mg, 79 % MS (Ti,Zr) ( Rh,Ru) [3 ], (70 ev,ci/ ) m/ z : 643 (C 36 H 30 ZrV + C 3 H 5 ), 422 (C 26 H 20 Zr + H), 182 (C 10 H 10 V + H) ; Raman :, 1570 (s,c C), 1550 ( sh,c Cph) cm - 1 Anal [ Cl 3 TiCl 3 VCl 3 ] ( PPh 4 ), calcd for C 36 H 30 ZrV ( M = 60418 g mol - 1 ) : C 71149,H [ (Cl) (aceacen) V2O2TiCl 3 ( THF) 2 ] [ aceacen 4195, Zr 15108, V 8142 ; found C 7112, H 511, Zr = N, N 2 ( ) ] [4 ] ( t2bu2 5 2 1518,V 810 C 5 H 4 ) 2 Zr ( 1 21, 1 21 ) ( 6 2C 6 H 5 ) 2 V [5 ], 1 2 Ti2V, (CNRS) 1 [ Cp 2 M ( C CPh) 2 ] Cp 2 V Ti2V Zr2V, Faraday,IR Perkin2Elmer : 4 2PhC 4 Ph) MCp 2 ] 1 (M = Ti), 2 (M 983G,Raman XYDILOR NMR = Zr), 2 X, Bruker AC200 113 (10 ml),,,, 910 mg( 90 %) ; MS (70 ev,ci/ ) m/ z : 562 (C 36 H 30 TiV + H), 381 (C 26 2 H 20 Ti + H),182 ( C 10 H 10 V + H) ; Raman : 1570 (s,c C),1550 (sh,c Cph) cm 21 Anal calcd for Nermag,R1010 2 X STOE IPDS, 1 1 Table 1 Crystal data and structure analysis parameters C 36 H 30 ZrV 600198 / mm 015 0135 011 P2 1 1 a/ nm b/ nm 0178453(8) 116744 (2) c/ nm 117981 (3) 1 1 216248 (1) Z 4 Schlenk F(000) 1200 (Vacuum atmosphere Dry2lab) D c / (g cm - 3 ) 11521 / cm, 612 T/ K 160, [ Cp 2 V ] [6 ], [ Cp 2 Ti (C 2 / ( ) 219 4814 CPh) 2 ] [7 ] 16424 [ Cp 2 Zr (C CPh) 2 ] [8 ] 4082 [ Cp 2 V ( 2 : 2PhC 4 Ph) TiCp 2 ] 1, ( F 2 ) GOF 1 02 [Cp 2 Ti ( C CPh) 2 ] (700 mg, 118 mmol) (10 R 0 085 ml) Cp 2 V(332 mg,118 mmol) R w 0 097 (min/ max) / (e nm - 3 ) 2 280/ 560 C 36 H 30 TiV ( M = 56115 g mol 21 ) : C 77101, H 5138, Ti 8153,V 9108 ; found C 7615, H 514, Ti 819, V 815 2 1 [Cp 2 V ( 2 4 2PhC 4 Ph) ZrCp 2 ] 2, [7 11 Cp 2 V (51 mg, 0128 mmol) (10 ml) ],Lang [12 [ Cp 2 Zr (C CPh) 2 ] (120 mg, 0128 mmol) Ti2Ag Ti2Cu ] [ Cp 2 Hf (C CPh) 2 ] (5 ml), 5, [Cp 2 Zr ( ) ] [ Cp 2 Hf ( 2
No 4 : 4 2PhC 4 Ph) MCp 2 ] (M = Ti,Zr) 689 C CPh) 2 ZrCp 2 ] [10 ],[ Cp 2 V( 2 2R 1 CCR 2 ) ] (R 1 = R 2 = Ph) Cp 2 V R 1 C CR 2 ( ) (C = C) 2 1165 B [13 ] 2 IR, (C C) 1570 (sh) 1550 (s) cm - 1 2 2 2 1, 2, Ti2V Zr2V,[ Cp 2 Ti (C CPh) 2 ] [ Cp 2 Zr2 (C CPh) 2 ] Cp 2 V, 90 % 80 % 1 2 1 1 2 ORTEP, THF Figure 1 Molecular structure and atom2numbering scheme for, compound 2 C 36 H 30 TiV IR, [ Cp 2 Ti (C CPh) 2 ] C C 2065 cm - 1 [7 ],C C 1960 1850 cm - 1 [9,12 ] 1 C C C(121) C(2) C(4) C(111) 133 ] 1 1173 B, C C, 2 :,V Cp 2 V (C CPh) V C(1) V C(2) [14 1 IR (C C) V C ],C (1) C (2) [14 C C ], (01144 nm) C C, C C,,, [ Cp 2 Ti (C CPh) 2 ] (C C) Zr 2070 cm - 1,1600 cm - 1 4 [15 2 ] C (1) C (3) C (2) C (4) 1 (C C), 1600 cm - 1 ( 01125 01127 nm) [ Cp 2 Zr2 (MeSiCCPh) (PMe, 3 ) ] C C C C, (2) 01233 (2) nm, [ Cp 2 ZrMe 2 ] 2090 cm - 1 C C, 1600 cm - 1 1570 1550 cm - 1 C C, 1,,1,,, Cp 2 V 360 [Cp 2 Zr (C CPh) [18 ] 2 ] 2, 2 Cp 2 V Cp 2 Zr C CPh [ C (1) C (3) 01125 01128 nm [13,14 ], [16 ] Zr C (3) Zr C (4) 01228 Zr C 01227 nm [17 ] Zr C (1) Zr C (2) 01232 01240 nm, Zr C (Cp) ( 0125 nm), [18 Zr ],C (1), C(2) [ Zr, V, C (2), C(3) Zr, V, C(1), C(4) ], C(2) C(3) C
690 Vol 60, 2002 Zr 4 C, [ Cp 2 Zr 1 2 NMR, 1 [ Cp 2 Zr (C CPh) 2 ], 2 Gauss 98, [ Cp 2 V ( 2 4 2PhC 4 Ph) ZrCp 2 ] 2, 2 3 (PhC 4 Ph) ], : Cp 2 V [ Cp 2 Zr (PhC 4 Ph) ] Cp 2 V( 1) 2 (nm) ( ) Table 2 Selected bond lengths (nm) and bond angles ( ) / nm / ( ) / ( ) Zr C(1) 01232 (2) C(1) Zr C(2) 3515 (6) Zr C(1) C(3) 73 (2) Zr C(2) 01240 (2) C(1) Zr C(3) 3116 (5) V C(1) C(3) 145 (2) Zr C(3) 01228 (2) C(2) Zr C(3) 6711 (7) C(1) C(2) C(4) 141 (3) Zr C(4) 01233 (2) C(1) Zr C(4) 6410 (7) Zr C(1) V 142 (2) Zr Cp (1) 0122 (av) C(2) Zr C(4) 2816 (7) Zr C(4) C(2) 79 (2) Zr Cp (2) 0122 (av) C(3) Zr C(4) 9517 (8) V C(1) C(2) 67 (2) V C(1) 01210 (2) Cp (1) Zr Cp (2) 133 (av) Zr C(3) C(1) 76 (2) V C(2) 01203 (2) C(1) V C(2) 4018 (7) V C(2) C(4) 147 (2) V Cp (3) 119 (av) Cp (3) V Cp (4) 142 (av) C(2) C(1) C(3) 148 (2) V Cp (4) 119 (av) Zr C(1) C(2) 76 (2) Zr C(2) C(4) 73 (2) C(1) C(2) 01144 (2) Zr C(3) C(121) 152 (2) Zr C(4) C(111) 148 (2) C(1) C(3) 01125 (2) C(1) C(3) C(121) 133 (2) C(2) C(4) C(111) 133 (3) C(2) C(4) 01127 (3) Zr C(2) V 14310 (2) C(3) C(121) 01151 (2) Zr C(2) C(1) 69 (2) C(4) C(111) 01147 (2) V C(2) C(1) 72 (2) 1 2 Scheme 1 The synthesis reaction mechanism of the compound 2
No 4 : 4 2PhC 4 Ph) MCp 2 ] (M = Ti,Zr) 691 6 Eisch, J J ; King, R B Organometal Synth Trans Met 3 Chem 1979, 182, 353 [ Cp 2 M ( C CPh) 2 ] Cp 2 V, 9 Janssen, M D ; Herres, M ; Zsolnai, L ; Grove, D M ; Ti (Zr)2V 1, 2 2 Spek, A L ; Lang, H ; van Koten, G Organometallics, 2, C Cp 2 V, C C Cp 2 Zr 11 Rosenthal, U ; Ohff, A ; Baumann, W Organometallics C 1994, 13, 2903 12 Lang, H ; Herres, M ; Zsolnai, L Organometallics 1993, 12, 5008 13 Fachinetti, G ; Floriani, C ; Chiesi2Villa, A Inorg Chem References 1 Fisher, R A ; Scherer, W ; Kleine, M Angew Chem, Int Ed Engl 1993, 32, 748 2 Baker, R T ; Fultz, W C ; Morder, T B Organometallics 1990, 9, 2357 3 Choukroun, R ; Iraqi, A ; Gervais, D Organometallics 1987, 6, 1197 4 Mazzanti, M ; Floriani, C ; Chiesi2Villa, A Inorg Chem 1986, 25, 4158 5 Elschenbroich, C ; Schmidt, E ; Metz, B Organometallics 1995, 14, 4043 Compounds, Academic Press, New York, 1965, pp 64 66 7 Teuben, J H ; De Liefde Meijer, H J J Organometal Chem 1969, 17, 8 8 Jimenez, R ; Barral, M C ; Moreno, V J Organometal 1995, 14, 1098 10 Erker, G ; Fromberg, W ; Mynott, R Angew Chem, Int Ed Engl 1986, 25, 463 1979, 18, 2282 14 Choukroun, R ; Donnadieu, B ; Malfant, I J Chem Soc, Chem Commun 1997, 2315 15 Erker, G ; Wicher, J ; Engel, K J Am Chem Soc 1980, 102, 6344 16 Rosenthal, U ; Ohff, A ; Michalik, M Angew Chem, Int Engl 1993, 32, 1193 17 Erker, G ; Kropp, K ; Atwood, J L Organometallics 1983, 2, 1551 18 Roettger, D ; Erker, G ; Froehlich, R ; Grehl, M ; Silverio, S J ; Gleiter, R J Am Chem Soc 1995, 117, 10503 (A0108248 SHEN, H )
Graphical Abstract Vol 60, No 4 Study on the Synthesis, Anti2cancer Activity and the Interaction with DNA of Compounds [ Pd( L) ( trp) ] Cl 5 H 2 O ( L = phen, 52NO 2 2 phen) GAO, En2Jun ; LIU, Qi2Tao Acta Chimica Sinica 2002, 60 (4), 674 When the compounds, [ Pd ( phen) 2 (trp ) ] Cl 5H 2 O ( 1) and [ Pd ( 52 NO 2 phen) (trp) ]Cl 5H 2 O (2), cause the emission of the system ( EtBr/ DNA) decreasing by half ( i e F/ F 0 = 50 %), the ratios ( C M / C DNA ) are 20 and 60, respectively This results show that the binding is mainly by intercalation mode with binding intensity of 1 > 2, which is in line with the binding constants and the anti2cancer activity Structure and Chemical Bonding Behavior of ( RXNR) 4 ( X = B, Al, Ga) Clusters WU, Hai2Shun ; ZHANG, Cong2Jie ; XU, Xiao2 Hong ; ZHANG, Fu2Qiang Acta Chimica Sinica 2002, 60 (4), 681 The optimized geometries, electron structure and bonding behavior of ( RXNR) 4 ( X = B, Al, Ga ; R = H, CH 3, NH 2, OH) were investigated by density functional theory (DFT) at the B3LYP/ 62311G 3 level The results show that (RXNR) 4 has a ring2sketch structure, while both ( RAlNR ) 4 and (RGaNR) 4 have cube2sketch ones Novel Heterometallic Complexes 2 : 4 2butadiyne) MCp 2 ] ( M = Ti, Zr) ZHAO, Jian2She ; GU, Ai2Ping ; HE, Shui2 Yang; CHOUKROUN, Robert ; VALADE, Lydie ; CASSOUX, Patrick Acta Chimica Sinica 2002, 60 (4), 687 The reaction of [ Cp 2 Ti (C CPh) 2 ], [ Cp 2 Zr (C CPh) 2 ] with vanadocene in toluene at room temperature gives heterodimetallic complexes [ Cp 2 V ( 2 butadiyne) MCp 2 ] 1 (M = Ti), 2 (M = Zr), respectively 4 2 Microbial Based Sensor for the Measurement of Glucose in Serum and Urine ZHU, Long ; LI, Yuan2Zong ; CI, Yun2Xiang Acta Chimica Sinica 2002, 60 (4), 692 A microbial based cytosensor can produce glucose oxidase that can catalyze the oxidation of glucose in the samples to produce hydrogen peroxide The hydrogen peroxide then oxidize a fluorogenic substrate in the presence of a mimetic enzyme Glucose in the samples can be determined according to the fluorescence intensity of the reaction product