Molybdenum complexes with tridentate NS2 ligands.: Synthesis, crystal structures and spectroscopic properties

被引:36
作者
Stelzig, L [1 ]
Kotte, S [1 ]
Krebs, B [1 ]
机构
[1] Univ Munster, Inst Anorgan Chem, D-48149 Munster, Germany
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1998年 / 17期
关键词
D O I
10.1039/a802334d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of the new tridentate NS, ligands 2-HSC6H4C(Me)=NNHC(S)SCH2Ph (H2L1), 2-HSC6H4C(Me)=NNHC(S)NHCPh3 (H2L2), 2-HSC6H4CH=NNHC(S)NHCPh3 (H2L3) and 1-Ph-3-Me-5-HS-C3N2-CH=NNC(SH)-NHCPh3 (H2L4) with dioxomolybdenum(VI) precursors yielded mononuclear molybdenum(VI) complexes [MoO2(L-1)(pic)] 1 (pic = 4-methylpyridine), [MoO2L2(MeOH)]. 2.25 MeOH 2 and the dinuclear molybdenum(v) complexes [Mo2O3L23]. 3CH(2)Cl(2) 3 and [Mo2O3L24] 4. The molecular structures of 1-3 were determined by single-crystal X-ray analysis. Complexes 1 and 2 each consist of a central cis-MoO2 unit with a mer co-ordinating tridentate dianionic ligand and one neutral donor molecule completing the octahedral environment of molybdenum(VI). Complex 3 exhibits an anti-Mo2O3 group co-ordinated by two mer chelating ligands. The symmetry-related molybdenum(v) centres are in a square pyramidal environment. Infrared, NMR and MS studies evidenced a comparable structure for 4. The reduction of the dioxomolybdenum(VI) compounds 1 and 2, achieved by addition of phosphines like PPh3, also leads to dinuclear mu-oxo-bridged complexes. The reverse oxidations of the oxomolybdenum(v) complexes are restricted by the nature of the ligand and the oxidizing agents.
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页码:2921 / 2926
页数:6
相关论文
共 25 条
[11]   OXOMOLYBDENUM(IV,V,VI) COMPLEXES - STRUCTURES, REACTIVITIES, AND CRITERIA OF DETECTION OF BINUCLEAR (MU-OXO)MOLYBDENUM(V) PRODUCTS IN OXYGEN ATOM TRANSFER SYSTEMS [J].
CRAIG, JA ;
HARLAN, EW ;
SNYDER, BS ;
WHITENER, MA ;
HOLM, RH .
INORGANIC CHEMISTRY, 1989, 28 (11) :2082-2091
[12]   Reactivity of Mo-O-t terminal bonds toward substrates having simultaneous proton- and electron-donor properties: A rudimentary functional model for oxotransferase molybdenum enzymes [J].
Dutta, SK ;
McConville, DB ;
Youngs, WJ ;
Chaudhury, M .
INORGANIC CHEMISTRY, 1997, 36 (12) :2517-2522
[13]  
GARNER CD, 1985, MOLYBDENUM ENZYMES, P343
[14]   THE BIOLOGICALLY RELEVANT OXYGEN ATOM TRANSFER CHEMISTRY OF MOLYBDENUM - FROM SYNTHETIC ANALOG SYSTEMS TO ENZYMES [J].
HOLM, RH .
COORDINATION CHEMISTRY REVIEWS, 1990, 100 :183-221
[15]   METAL-CENTERED OXYGEN ATOM TRANSFER-REACTIONS [J].
HOLM, RH .
CHEMICAL REVIEWS, 1987, 87 (06) :1401-1449
[16]   STUDIES OF THIOACIDS AND THEIR DERIVATIVES .9. THIOSEMICARBAZIDES [J].
JENSEN, KA ;
ANTHONI, U ;
KAGI, B ;
LARSEN, C ;
PEDERSEN, CT .
ACTA CHEMICA SCANDINAVICA, 1968, 22 (01) :1-&
[17]  
KASMAI HS, 1989, SYNTHESIS-STUTTGART, P763
[18]   DEPROTONATED THIOAMIDES AS THIOLATE S-DONOR LIGANDS WITH A HIGH TENDENCY TO AVOID M-S-M BRIDGE FORMATION - CRYSTAL AND MOLECULAR-STRUCTURE OF [NI(TMTSSA)]2 [J].
LU, Z ;
WHITE, C ;
RHEINGOLD, AL ;
CRABTREE, RH .
INORGANIC CHEMISTRY, 1993, 32 (19) :3991-3994
[19]   TRANSITION-METAL COMPLEXES OF SEMICARBAZONES AND THIOSEMICARBAZONES [J].
PADHYE, S ;
KAUFFMAN, GB .
COORDINATION CHEMISTRY REVIEWS, 1985, 63 (APR) :127-160
[20]   CHEMISTRY OF MOLYBDENUM WITH HARD-SOFT DONOR LIGANDS .2. MOLYBDENUM(VI), MOLYBDENUM(V), AND MOLYBDENUM(IV) OXO COMPLEXES WITH TRIDENTATE SCHIFF-BASE LIGANDS [J].
PUROHIT, S ;
KOLEY, AP ;
PRASAD, LS ;
MANOHARAN, PT ;
GHOSH, S .
INORGANIC CHEMISTRY, 1989, 28 (19) :3735-3742