Coordination chemistry of polyoxomolybdates: The versatile behavior of amidoximes |
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Authors: | Soo-Gyun Roh Anna Proust Francis Robert Pierre Gouzerh |
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Affiliation: | (1) KyungPook National University, Republic of Korea;(2) Laboratoire de Chimic des Metaux de Transition, URA-CNRS, No. 419, Unversité Pierre et Marie Curie,, Case 42. 4 Place Jussieu, 75252 Paris Cedex 05, France |
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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)22 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, =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. =92.67(2)c =99.36(1)° =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- O, 2N,O, 2N',O, µ-N: 2O. and 3- N:N:2O. |
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Keywords: | Molybdenum polyoxometalates metal oxide analogs amidoximes hydroxylaminc nitrosyl complexes |
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