Polymetallic clusters of iron(III) with derivatised salicylaldoximes.
The synthesis and magnetic properties of the compounds [HNEt(3)][Fe(2)(OMe)(Ph-sao)(2) (Ph-saoH)(2)].5MeOH (1.5MeOH), [Fe(3)O(Et-sao)(O(2)CPh)(5)(MeOH)(2)].3MeOH (2.3MeOH), [Fe(4)(Me-sao)(4)(Me-saoH)(4)] (3), [HNEt(3)](2)[Fe(6)O(2)(Me-sao)(4)(SO(4))(2)(OMe)(4)(MeOH)(2)] (4), [Fe(8)O(3)(Me-sao)(3)(tea)(teaH)(3)(O(2)CMe)(3)] (5), [Fe(8)O(3)(Et-sao)(3)(tea)(teaH)(3)(O(2)CMe)(3)] (6), and [Fe(8)O(3)(Ph-sao)(3)(tea)(teaH)(3)(O(2)CMe)(3)] (7) are reported (Me-saoH(2) is 2'-hydroxyacetophenone oxime, Et-saoH(2) is 2'-hydroxypropiophenone oxime and Ph-saoH(2) is 2-hydroxybenzophenone oxime). 1-7 are the first Fe(III) compounds synthesised using the derivatised salicylaldoxime ligands, R-saoH(2). 1 is prepared by treatment of Fe(2)(SO(4))(3).6H(2)O with Ph-saoH(2) in the presence of NEt(3) in MeOH; 2 prepared by treatment of Fe(ClO(4))(2).6H(2)O with Et-saoH(2) and NaO(2)CPh in the presence of NEt(4)OH in MeOH; 3 prepared by treatment of Fe(ClO(4))(2).6H(2)O with Me-saoH(2) and NaO(2)CCMe(3) in the presence of NEt(4)OH in MeOH; and 4 prepared by treatment of Fe(2)(SO(4))(3).6H(2)O with Me-saoH(2) in the presence of NEt(3) in MeOH. 4 is a rare example of a polynuclear iron complex containing a coordinated SO(4)(2-) ion. Compounds 5-7 are prepared by treatment of Fe(O(2)CMe)(2) with Me-saoH(2) (5), Et-saoH(2) (6), Ph-saoH(2) (7) in the presence of H(3)tea (triethanolamine) in MeOH, and represent the largest nuclearity Fe(III) clusters containing salicyladoxime-based ligands, joining a surprisingly small family of characterised octanuclear Fe complexes. Variable temperature magnetic susceptibilty measurements of 1, 3 and 5-7 reveal all five complexes possess S = 0 spin ground states; 2 possesses an S = 1/2 spin ground state, while 4 has an S = 4 +/- 1 spin ground state.
Gass
Ian A
IA
School of Chemistry, The University of Edinburgh, West Mains Road, Edinburgh, UK EH9 3JJ.
Milios
Constantinos J
CJ
Collins
Anna
A
White
Fraser J
FJ
Budd
Laura
L
Parsons
Simon
S
Murrie
Mark
M
Perlepes
Spyros P
SP
Brechin
Euan K
EK
D002412:Cations / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D006860:Hydrogen Bonding; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D000432:Methanol / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D010091:Oximes / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013431:Sulfates / Q000737:chemistry; D013696:Temperature
D002412:Cations; D008024:Ligands; D009942:Organometallic Compounds; D010091:Oximes; D012997:Solvents; D013431:Sulfates; C005704:salicylaldoxime; D003300:Copper; D007501:Iron; D000432:Methanol