Cyanidhaltige metallorganische cyclopentadienylver bindungen der lanthanoide und actinoide

Kanellakopulos, Β.; Dornberger, E.; Billich, H.

doi:10.1016/s0022-328x(00)87390-8

Cited by 55 publications

(23 citation statements)

References 7 publications

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“…27 The tris(cyclopentadienyl) and bis-(indenyl) cerium(IV) complexes [Ce(Cp) 3 (CN)] (Cp = η-C 5 H 5 ) and [Ce(C 9 H 7 ) 2 (CN) 2 ] were reported in 1972, 28 but these results were strongly questioned. 29 30 Other syntheses of the tris(cyclopentadienyl) derivatives [U(C 5 H 4 R) 3 (CN)] were proposed afterwards (Scheme 1): from salt metathesis reactions of [U(C 5 H 4 R) 3 Cl] (R = H, Me) with alkali metal cyanides in aqueous solution or acetonitrile, 31 oxidation of [U(C 5 H 4 R) 3 ] (R = H, t Bu) with nitrile 32 or isonitrile molecules, 30,31 and addition of N n Bu 4 CN to the cationic precursors [U(C 5 H 4 R) 3 ][BPh 4 ] (R = t Bu, SiMe 3 ). 33,34 However, attempts at the preparation of the anionic derivatives [U(C 5 H 4 R) 3…”

Section: Pierre Thuérymentioning

confidence: 99%

Advances in f-element cyanide chemistry

2015

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This Dalton perspective gives an overview of the development of cyanide chemistry of 4f- and 5f-elements, a field which was poorly explored in contrast to the attention paid to the cyanide complexes of the d transition metals. The use of the cyanide ligand led to the discovery of mono- and polycyanide complexes which exhibit unprecedented and unexpected coordination geometries. A new type of linear metallocenes including [U(Cp*)2(CN)5](3-) (Cp* = C5Me5) and the first bent actinocenes [An(Cot)2(CN)](-) (An = Th, U; Cot = C8H8) were isolated. Thorocene was found to be much more reactive than uranocene since a series of sterically crowded cyanide complexes have been obtained only from [Th(Cot)2]. A series of cyanido-bridged dinuclear compounds and mononuclear mono-, bis- and tris(cyanide) complexes were prepared by addition of cyanide salts to [MN*3] (M = Ce, U) and [UN*3](+) [N* = N(SiMe3)2]. The Ce(III), U(III) and U(IV) ions were clearly differentiated in these reactions by cyanide linkage isomerism, as shown for example by the structures of the cyanide complex [U(III)N*3(CN)2](2-) and of the isocyanide derivatives [Ce(III)N*3(NC)2](2-) and [U(IV)N*3(NC)](-). While the U-CN/NC coordination preference towards the U(III)/U(IV) pair is related to the subtle balance between steric, covalent and ionic factors, DFT computations and in particular the calculated total bonding energies between the metal and the cyanide ligand allowed the observed coordination mode to be predicted. The ability of the cyanide ligand to stabilize the high oxidation states was assessed with the synthesis of U(V) and U(VI) complexes in the inorganic and organometallic series.

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Section: Pierre Thuérymentioning

confidence: 99%

Advances in f-element cyanide chemistry

2015

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“…While a multitude of cyanide complexes of the transition metals are known [1,2], only a few cyanido complexes of uranium(IV) have been reported [3][4][5][6][7][8][9][10]. The first actinoid compound containing cyanide anions was K 2 [UO 2 (CN) 4 ] described by Aloy, followed by K 2 [UO 2 (CN) 2 (NO 3 ) 2 ] [11,12].…”

Section: Introductionmentioning

confidence: 99%

A spatially separated [KBr₆]⁵⁻ anion in the cyanido-bridged uranium(IV) compound [U₂(CN)₃(NH₃)₁₄]⁵⁺[KBr₆]⁵⁻·NH₃

Deubner

Kraus

2019

Zeitschrift Für Naturforschung B

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The reaction of uranium tetrabromide with potassium cyanide in anhydrous liquid ammonia at room temperature leads to the formation of brown crystals of [U2(CN)3(NH3)14]5+ [KBr6]5− · NH3. We determined the crystal structure of the compound by single crystal X-ray diffraction. To the best of our knowledge it contains the unprecedented spatially separated [KBr6]5− anion and presents the first uranium(IV) cyanide compound which forms a layer structure. The compound crystallizes in the trigonal space group P3̅m1 (No. 164) with a = 10.3246(13), c = 8.4255(17) Å, V = 777.8(3) Å3, Z = 1 at T = 100 K and is well described with the Niggli formula $\mathop {} \limits_{\infty}^{2}{\left[ {{\rm{U}}{{({\rm{CN}})}_{{3 \over 2}}}{{({\rm{N}}{{\rm{H}}_3})}_{{7 \over 1}}}} \right]_2}\left[ {{\rm{KB}}{{\rm{r}}_{{6 \over 1}}}} \right].$

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“…1 However, it is rather surprising that cyano compounds of these elements are practically unknown, being limited for the actinides to a few U(III) and U(IV) species with only two recently structurally characterized tetravalent organometallic species. [2][3][4][5][6][7][8] This situation is in striking contrast to that encountered with the d-transition metal complexes where the CN 2 group occupies a prominent position in various domains, from biology to materials science. 9 The strong coordinating ability of the CN 2 ion which can adopt several ligation modes, 9 gave rise to a large number of homo-and hetero-polynuclear complexes which exhibit a rich variety of structures and unusual physicochemical properties, as recently highlighted with the fascinating magnetic behaviour of Prussian Blue type complexes.…”

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“…This value is smaller than that found in the neutral parent UO 2 (OTf) 2 (982 cm 21 ) but is in the range of frequencies (904-923 cm 21 ) found in the electron rich species [UO 2 X 4 ] 22 (X = Cl, Br). 15 The two major n(CN) absorption bands at 2190 and 2180 cm 21 can be compared with those in the organometallic complexes Cp 2 UCN (2112 cm 21 ), 7 Cp 3 UCN (2116 cm 21 ) 7 (1,2,4-Bu t 3 C 5 H 2 ) 2 U-(OSiMe 3 )(CN) (2040 cm 21 ), 3 Cp 2 LnCN (2187 and 2116 cm 21 for Ln = Nd; 2198 and 2136 cm 21 for Ln = Yb). 7 The highest n(CN) values for the 5f 0 uranyl compound can be tentatively explained by the absence of p-back donation from the U 6+ ion to the cyanide ligand which might occur with the lower valent U 3+ and U 4+ ions.…”

mentioning

confidence: 99%