ISSN:
1572-8862
Schlagwort(e):
Molybdenum
;
polyoxometalates
;
metal oxide analogs
;
amidoximes
;
hydroxylaminc
;
nitrosyl complexes
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Maschinenbau
,
Physik
Notizen:
Abstract The reactions of 2-thienylamidoxime and 2-thienylmethylamidoxime with [MoO2(acae)2] or x-(NBu4 [Mo8O26]. in alcohols or acetonitrile, yield a number of compounds with different nuclearities and various molybdenum cores, such as the compact {Mo4O10(OMe)2}2+ the cyclic {Mo4O12}, and the open {Mo11On211-1}2+ (n= 2 or 4) cores. Addition of NH2OH to the reaction mixtures results in the formation of nitrosyl complexes containing either the Mo(NO)3 or the Mo(NO) 2 2 units. The amidoxime component may be present either as RC(NH2)NHO. RC(NHi2), RC(NH)NHO or RC(NH)NO2: ligands, or as hydrogen-bonded RC(NH2)NOH molecules. The crystal structures of [MoO(acac)RIC'(NH2)NO] {RJC(NH)NO}](1), [Mo(NO)(acae)2 {RIC(NH2)NO}] (4), (NBu4)2[Mo4O10(OMe)2{RIC(NH) NO}2] (12a),(NBu4)2(H3O)[Mo5O13(OMe)4(NO)].2R1C(NH2)NOH(13b) and [R1C(NH2)2)]3[Mo5O13(OEt)4(NO)] (14) (R1=2-thienyl) are reported. The cryslallographic data for these compounds are as follows:1, mono-clinic. P21 a.a=24.547(4)A. b=8.188(4)A. c=9.607(3)A, ß=96.18(3)c, R=0.046. R10=0.050: 4. monoclinic, P21c.a=8.265(2)A, b=9.381(2)A,c=24.770(4)A, c = 24.7701(4) A, ß=93.99(2). R=0.039. R=0.042;12a, monoclinic, C2/c, a= 19.570(5)A. b=16.883(4)A, c = 19.82(l)A. ß= 114.36(5)°, R=0.064,R.=0.074;13b monoclinic;. P21 c.a=18.197(5)A, b=15.857(14) A, c = 23.075(17) A, β=93.20(3). R=O.050. Rw=0.057;14, trictinic PI, a = 9.871(3),b= 14.138(3).c= 14.781(8)A. α=92.67(2)c β=99.36(1)° γ=90.52(2)°. R = 0.044. Rw = 0.049. Particular attention is focused on the various coordination modes that the different ligand forms adopt: µ- κO, κ2N,O, κ2N',O, µ-κN: κ2O. and μ3- κN:κN:κ2O.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/BF01165804
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