ISSN:
1432-1327
Keywords:
Key words Oxotungsten complexes
;
Tungsten enzymes
Source:
Springer Online Journal Archives 1860-2000
Topics:
Biology
,
Chemistry and Pharmacology
Notes:
Abstract Synthesis of complexes cis,cis-WVOXL (X=Cl, NCS), cis,trans-WVOXL (X=Cl, OPh, SPh) and cis,trans-WVIE2L (E2=O2, OS, S2) of the title ligand LH2 are reported. cis,cis-WVOCIL crystallises in space group P21/c with a=13.6541(9) Å, b=7.1555(11) Å, c=18.198(2) Å, β=95.294(6)°, V=1770.4(3) Å3 and Z=4 while the cis,trans isomer crystallises in space group P21/n with a=10.361(3) Å, b=14.141(4) Å, c=12.213(5) Å, β=102.56(3)°, V=1747(2) Å3 and Z=4. cis,trans-WVIS2L crystallises in space group P21/n with a=10.645(2) Å, b=13.929(2) Å, c=12.189(2) Å, β=103.14(2)°, V=1760(1) Å3 and Z=4. A short CH3···Cl distance of 3.067(7) Å and an acute OWCl angle of 94.1(2)° are seen in cis,cis-WVOClL, which converts to the cis,trans form on heating in MeCN. The latter isomer features a CH3···Cl distance of 3.38(2) Å and an OWCl angle of 105.1(8)°. Electrochemical and EPR data are reported. In particular, cis,trans-WVIE2L may be reduced to [WVE2L]–. EPR properties of these anions and those of complexes WVOXL are discussed in the context of WV centres in tungsten enzymes.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/s007750050177
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