Synthesis of oxomolybdenum bis(dithiolene) complexes related to the cofactor of the oxomolybdoenzymes

被引:91
作者
Davies, ES [1 ]
Beddoes, RL [1 ]
Collison, D [1 ]
Dinsmore, A [1 ]
Docrat, A [1 ]
Joule, JA [1 ]
Wilson, CR [1 ]
Garner, CD [1 ]
机构
[1] UNIV MANCHESTER,DEPT CHEM,MANCHESTER M13 9PL,LANCS,ENGLAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1997年 / 21期
关键词
D O I
10.1039/a703682e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A synthetic strategy is reported for a general route to asymmetric dithiolenes. This has been used for the generation of [MoO(dithiolene)(2)](2-) complexes [dithiolene = -SC(H)C(R)S-, R = phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, quinoxalin-2-yl or 2-(dimethylaminomethyleneamino)-3-methyl-4-oxopteridin-6-yl], which have been characterised by analysis, spectroscopy and electrochemistry. The prototypical compound [PPh4](2)[MoO(sdt)(2)].EtOH, where sdt = alpha,beta-styrenedithiolate (R = phenyl), crystallises in the space group P2(1)/c with a = 13.217(4), b = 31.820(8), c = 14.534(7) Angstrom, beta = 113.8(2)degrees and Z = 4. The MoOS4 moiety is square-based pyramidal with the O atom at the apex [Mo = O, 1.700(5) Angstrom] and contains a cis geometry of the phenyl groups. The physical properties of all the compounds are consistent with a retention of the MoOS4 centre and the variation in the dithiolene H-1 NMR resonances, infrared v(Mo=O) and v(C=C) stretching frequencies and the E-1/2 values for the Mo-V-Mo-IV couple are rationalised by a consideration of the nature of the R substituent. The complexes with the pterin [2-amino-4(1H)-pteridinone] substituent have a particular relevance to the Mo centre in oxomolybdoenzymes, and are the closest structural models to date for these enzymes containing two molybdopterin ligands per metal.
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页码:3985 / 3995
页数:11
相关论文
共 56 条
  • [1] HALIDE AND OXYHALIDE COMPLEXES OF MOLYBDENUM AND TUNGSTEN
    ALLEN, EA
    WILLIAMS, RG
    EDWARDS, DA
    BRISDON, BJ
    FOWLES, GWA
    [J]. JOURNAL OF THE CHEMICAL SOCIETY, 1963, (OCT): : 4649 - &
  • [2] [Anonymous], ADV INORG CHEM
  • [3] Preliminary crystallographic studies of dimethylsulfoxide reductase from Rhodobacter capsulatus
    Bailey, S
    McAlpine, AS
    Duke, EMH
    Benson, N
    McEwan, AG
    [J]. ACTA CRYSTALLOGRAPHICA SECTION D-BIOLOGICAL CRYSTALLOGRAPHY, 1996, 52 : 194 - 196
  • [4] Bailey S., UNPUB
  • [5] MULTIPLE STATES OF THE MOLYBDENUM CENTER OF DIMETHYLSULFOXIDE REDUCTASE FROM RHODOBACTER-CAPSULATUS REVEALED BY ER SPECTROSCOPY
    BENNETT, B
    BENSON, N
    MCEWAN, AG
    BRAY, RC
    [J]. EUROPEAN JOURNAL OF BIOCHEMISTRY, 1994, 225 (01): : 321 - 331
  • [6] DETECTION OF THE OPTICAL BANDS OF MOLYBDENUM(V) IN DMSO REDUCTASE (RHODOBACTER-CAPSULATUS) BY LOW-TEMPERATURE MCD SPECTROSCOPY
    BENSON, N
    FARRAR, JA
    MCEWAN, AG
    THOMSON, AJ
    [J]. FEBS LETTERS, 1992, 307 (02) : 169 - 172
  • [7] GENERAL SYNTHESIS OF 1,3-DITHIOL-2-ONES
    BHATTACHARYA, AK
    HORTMANN, AG
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (01) : 95 - 97
  • [8] A NEW SYNTHETIC ROUTE TO TRANSITION-METAL COMPLEXES OF UNSYMMETRICALLY SUBSTITUTED DITHIOLENES - EVIDENCE FOR A METALLADITHIOLENE RING CURRENT
    BOYDE, S
    GARNER, CD
    JOULE, JA
    ROWE, DJ
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (11) : 800 - 801
  • [9] STRUCTURAL COMPARISON OF OXOBIS(BENZENE-1,2-DITHIOLATO)MOLYBDENUM-(V) AND OXOBIS(BENZENE-1,2-DITHIOLATO)MOLYBDENUM-(IV) COMPLEXES
    BOYDE, S
    ELLIS, SR
    GARNER, CD
    CLEGG, W
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (20) : 1541 - 1543
  • [10] Crystal structure of formate dehydrogenase H: Catalysis involving Mo, molybdopterin, selenocysteine, and an Fe4S4 cluster
    Boyington, JC
    Gladyshev, VN
    Khangulov, SV
    Stadtman, TC
    Sun, PD
    [J]. SCIENCE, 1997, 275 (5304) : 1305 - 1308