Synthesis, crystal structure and reactivity of uranium(IV) complexes with p-tert-butylcalix[4]arene ligands

Reactions of UCl4 with 25,27-dimethoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (H2Me2calix) in THF or pyridine at 80 degrees C gave [UCl2(Me2calix)L2] [L = THF (1) or pyridine (2)]. Similar treatment of U(acac)(4) (acac = MeCOCHCOMe) with H2Me2calix in THF or pyridine afforded [U(acac)2(Me2calix)] (3). The bis-calixarene compound [U(Me2calix)(H2calix)] (4) was obtained by reaction of U(OTf)4 or U(OTf)3 with H2Me2calix in pyridine at 110 degrees C. Treatment of UCl4 with H2Me2calix in pyridine at 110 degrees C gave [Mepy][UCl2(Hcalix)(py)2] (5) resulting from demethylation and acid cleavage of the methoxy groups of the calixarene ligand of 2. Adventitious traces of air were responsible for the formation of [Hpy][Mepy]4[{UCl(calix)}3(mu3-O)][UCl6] (6) during the reaction of UCl4 and H2Me2calix, and of [{U(Me2calix)(mu3-O)LiCl(THF)}2] (7) during the reaction of 2 with tBuLi. The X-ray crystal structures of 1.2THF, 2.2py, 3.0.25L (L = THF and py), 4.2py, 5, 6.3py and 7.THF have been determined.     

(C5Me5)2U][(mu-Ph)2BPh2] as a four electron reductant

Examination of the reactivity of [(C5Me5)2U][(mu-Ph)2BPh2] as a "blank" for comparison with the four- and eight-electron reductive chemistry of the sterically crowded (C5Me5)3U and [(C5Me5)2U]2(C6H6) complexes revealed that the tetraphenylborate complex surprisingly functions as a four-electron reductant by combining [BPh4]1- and U(III) reduction; all three complexes cleave the N=N bond in PhN=NPh to form the bis(organoimido) U(VI) complex, (C5Me5)2U(NPh)2, and they also reduce PhC[triple bond]CPh to form (C5Me5)2U(C4Ph4).     

Trivalent [(C5Me5)2(THF)Ln]2(mu-eta2:eta2-N2) complexes as reducing agents including the reductive homologation of CO to a ketene carboxylate, (mu-eta4-O2C-C=C=O)2-

The [Z(2)Ln(THF)](2)(mu-eta(2)():eta(2)()-N(2)) complexes (Z = monoanionic ligand) generated by reduction of dinitrogen with trivalent lanthanide salts and alkali metals are strong reductants in their own right and provide another option in reductive lanthanide chemistry. Hence, lanthanide-based reduction chemistry can be effected in a diamagnetic trivalent system using the dinitrogen reduction product, [(C(5)Me(5))(2)(THF)La](2)(mu-eta(2)():eta(2)()-N(2)), 1, readily obtained from [(C(5)Me(5))(2)La][BPh(4)], KC(8), and N(2). Complex 1 reduces phenazine, cyclooctatetraene, anthracene, and azobenzene to form [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(12)H(8)N(2))], 2, (C(5)Me(5))La(C(8)H(8)), 3, [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(14)H(10))], 4, and [(C(5)Me(5))La(mu-eta(2)-(PhNNPh)(THF)](2), 5, respectively. Neither stilbene nor naphthalene are reduced by 1, but 1 reduces CO to make the ketene carboxylate complex {[(C(5)Me(5))(2)La](2)[mu-eta(4)-O(2)C-C=C=O](THF)}(2), 6, that contains CO-derived carbon atoms completely free of oxygen.     

Reductive cyclotetramerization of CO to squarate by a U(III) complex: the X-ray crystal structure of [(U (eta-C8H6{SiiPr3-1,4}2)(eta-C5Me4H)]2(mu-eta2: eta2-C4O4)

The U(III) mixed-sandwich compound [U(eta-C5Me4H)(eta-C8H6{SiiPr3-1,4}2)(THF)] 1 may be prepared by sequential reaction of UI3 with K[C5Me4H] in THF followed by K2[C8H6{SiiPr3-1,4}2]. 1 reacts with carbon monoxide at -30 degrees C and 1 bar pressure in toluene solution to afford the crystallographically characterized dimer [(U(eta-C8H6{SiiPr3-1,4}2)(eta-C5Me4H)]2(mu-eta2: eta2-C4O4) 2, which contains a bridging squarate unit derived from reductive cyclotetramerization of CO. DFT computational studies indicate that addition of a 4th molecule of CO to the model deltate complex [U(eta-COT)(eta-Cp)]2(mu-eta1: eta2-C3O3)] to form the squarate complex [U(eta-COT)(eta-Cp)]2(mu-eta2: eta2-C4O4)] is exothermic by 136 kJ mol-1.     

Synthesis and reactivity of bis(imido) uranium(VI) cyclopentadienyl complexes

The bis(imido) uranium(VI)-C(5)H(5) and -C(5)Me(5) complexes (C(5)H(5))(2)U(N(t)Bu)(2), (C(5)Me(5))(2)U(N(t)Bu)(2), (C(5)H(5))U(N(t)Bu)(2)(I)(dmpe), and (C(5)H(5))(2)U(N(t)Bu)(2)(dmpe) can be synthesized from reactions between U(N(t)Bu)(2)(I)(2)(L)(x) (L=THF, x=2; L=dmpe, x=1) and Na(C(5)R(5)) (R=H, Me); these complexes represent the first structurally characterized C(5)H(5)-compounds of uranium(VI) and they further highlight the differences between UO(2)(2+) and the bis(imido) fragment.     

Uranium (III) scorpionates: synthesis and structure of [(TpMe2)2U[N(C6H5)2]] and [(TpMe2)2U[N(SiMe3)2]

Reaction of [(Tp(Me)2)(2)UI] with KNR(2) (R = C(6)H(5), SiMe(3)) in tetrahydrofuran (THF) afforded the monomeric trivalent actinide amide complexes [(Tp(Me)2)(2)U[N(C(6)H(5))(2)]], 1, and [(Tp(Me)2)(2)U[N(SiMe(3))(2)]], 2. The complexes have been fully characterized by spectroscopic methods and their structures were confirmed by X-ray crystallographic studies. In the solid state 1 and 2 exhibit distorted pentagonal bipyramidal geometries. The U-NR(2) bond lengths in both complexes are the same but in complex 2 the greater steric demands of the N(SiMe(3))(2) ligand led to elongated U-N(pz) bonds, especially those opposite the amido ligand.     

Structure, reactivity, and density functional theory analysis of the six-electron reductant, [(C5Me5)2U]2(mu-eta6:eta6-C6H6), synthesized via a new mode of (C5Me5)3M reactivity

The sterically crowded (C(5)Me(5))(3)U complex reacts with KC(8) or K/(18-crown-6) in benzene to form [(C(5)Me(5))(2)U](2)(mu-eta(6):eta(6)-C(6)H(6)), 1, and KC(5)Me(5). These reactions suggested that (C(5)Me(5))(3)U could be susceptible to (C(5)Me(5))(1-) substitution by benzene anions via ionic salt metathesis. To test this idea in the synthesis of a more conventional product, (C(5)Me(5))(3)U was treated with KN(SiMe(3))(2) to form (C(5)Me(5))(2)U[N(SiMe(3))(2)] and KC(5)Me(5). 1 has long U-C(C(5)Me(5)) bond distances comparable to (C(5)Me(5))(3)U, and it too is susceptible to (C(5)Me(5))(1-) substitution via ionic metathesis: 1 reacts with KN(SiMe(3))(2) to make its amide-substituted analogue [[(Me(3)Si)(2)N](C(5)Me(5))U](2)(mu-eta(6):eta(6)-C(6)H(6)), 2. Complexes 1 and 2 have nonplanar C(6)H(6)-derived ligands sandwiched between the two uranium ions. 1 and 2 were examined by reactivity studies, electronic absorption spectroscopy, and density functional theory calculations. [(C(5)Me(5))(2)U](2)(mu-eta(6):eta(6)-C(6)H(6)) functions as a six-electron reductant in its reaction with 3 equiv of cyclooctatetraene to form [(C(5)Me(5))(C(8)H(8))U](2)(mu-eta(3):eta(3)-C(8)H(8)), (C(5)Me(5))(2), and benzene. This multielectron transformation can be formally attributed to three different sources: two electrons from two U(III) centers, two electrons from sterically induced reduction by two (C(5)Me(5))(1-) ligands, and two electrons from a bridging (C(6)H(6))(2-) moiety.     

Scandium and yttrium metallocene borohydride complexes: comparisons of (BH4)1- vs. (BPh4)1- coordination and reactivity

The synthetically accessible borohydride complexes (C(5)Me(4)H)(2)Ln(THF)(BH(4)) and (C(5)Me(5))(2)Ln(THF)(BH(4)) (Ln = Sc, Y) were examined as precursors alternative to the heavily-used tetraphenylborate analogs, [(C(5)Me(4)H)(2)Ln][BPh(4)] and [(C(5)Me(5))(2)Ln][BPh(4)], employed in LnA(2)A'/M reduction reactions (A = anion; M = alkali metal) that generate "LnA(2)" reactivity and form reduced dinitrogen complexes [(C(5)R(5))(2)(THF)(x)Ln](2)(μ-η(2):η(2)-N(2)) (x = 0, 1). The crystal structures of the yttrium borohydrides, (C(5)Me(4)H)(2)Y(THF)(μ-H)(3)BH, 1, and (C(5)Me(5))(2)Y(THF)(μ-H)(2)BH(2), 2, were determined for comparison with those of the yttrium tetraphenylborates, [(C(5)Me(4)H)(2)Y][(μ-Ph)(2)BPh(2)], 3, and [(C(5)Me(5))(2)Y][(μ-Ph)(2)BPh(2)], 4. The complex (C(5)Me(4)H)(2)Sc(μ-H)(2)BH(2), 5, was synthesized and structurally characterized for comparison with (C(5)Me(5))(2)Sc(μ-H)(2)BH(2), 6, [(C(5)Me(4)H)(2)Sc][(μ-Ph)BPh(3)], 7, and [(C(5)Me(5))(2)Sc][(μ-Ph)BPh(3)], 8. Structural information was also obtained on the borohydride derivatives, (C(5)Me(4)H)(2)Sc(μ-H)(2)BC(8)H(14), 9, and (C(5)Me(5))(2)Sc(μ-H)(2)BC(8)H(14), 10, obtained from 9-borabicyclo(3.3.1)nonane (9-BBN) and (C(5)Me(4)R)(2)Sc(η(3)-C(3)H(5)), where R = H, 11; Me, 12. The preference of the metals for borohydride over tetraphenylborate binding was shown by the facile displacement of (BPh(4))(1-) in 3, 4, 7, and 8 by (BH(4))(1-) to make the respective borohydride complexes 1, 2, 5, and 6. These results are consistent with the fact that the borohydrides are not as useful as precursors in A(2)LnA'/M reductions of N(2). An unusual structural isomer of [(C(5)Me(4)H)(2)Sc](2)(μ-η(2):η(2)-N(2)), 13', was isolated from this study that shows the variations in ligand orientation that can occur in the solid state.     

Facile syntheses of unsolvated UI3 and tetramethylcyclopentadienyl uranium halides

In the course of comparing the reaction chemistry of (C5Me5)3U, 1, and its slightly less crowded analogue (C5Me4H)3U, 2, new syntheses of UI3, (C5Me4H)3U, (C5Me4H)3UCl, 3, and (C5Me5)3UCl, 4, have been developed. Additionally, (C5Me4H)3UI, 5, and (C5Me4H)2UCl2, 6, have been identified for the first time. A facile synthesis of unsolvated UI3 is reported that proceeds in high yield with inexpensive equipment from iodine and hot uranium turnings. Both UI3 and UI3(THF)4 react with KC5Me4H in toluene to make unsolvated (C5Me4H)3U in higher yield than in previous reports that involve reduction of tetravalent (C5Me4H)3UCl, 3. A more atom-efficient synthesis of complex 3 is also reported that proceeds from reduction of t-BuCl, PhCl, or HgCl2 by 2. Similarly, (C5Me4H)3U reacts with PhI or HgI2 to generate (C5Me4H)3UI. These studies also provided a basis to improve the synthesis of (C5Me5)3UCl from 1 by employing t-BuCl or HgCl2 as the halide source. Like (C5Me5)3UCl, the (C5Me4H)3UCl complex reacts with HgCl2 to form (C5Me4H)2 and (C5Me4H)2UCl2, 6, but unlike (C5Me5)3UX (X = Cl or I), the less substituted (C5Me4H)3UX complexes do not reduce t-BuCl or PhX. The synthesis of 6 from (C5Me4H)MgCl x THF and UCl4 is also included.     

Synthesis of (C5Me5)2(C5Me4H)UMe, (C5Me5)2(C5H5)UMe, and (C5Me5)2UMe[CH(SiMe3)2] from cationic metallocenes for the evaluation of sterically induced reduction

To probe the correlation of unusual (C5Me5)(1-) reactivity with steric crowding in complexes such as (C5Me5)3UMe and (C5Me5)3UCl, slightly less crowded (C5Me5)2(C5Me4H)UX analogues (X = Me, Cl) were synthesized and their reactivity was evaluated. The utility of the cationic precursors [(C5Me5)2UMe](1+), 1, and [(C5Me5)2UCl](1+), 2, in the synthesis of (C5Me5)2(C5Me4H)UMe, 3, and (C5Me5)2(C5Me4H)UCl, 4, was also explored. Since the use of precursor [(C5Me5)2UMe][MeBPh3], 1a, is complicated by the equilibrium between 1a and (C5Me5)2UMe2/BPh3, the reactivity of [(C5Me5)2UMe(OTf)]2, 1b, (OTf = O3SCF3) prepared from (C5Me5)2UMe2 and AgOTf, was also studied. Both 1a and 1b react with KC5Me4H to form 3. Complex 4 readily forms by addition of KC5Me4H to [(C5Me5)2UCl][MeBPh3], generated in situ from (C5Me5)2UMeCl and BPh3. Complex 1b was preferred to 1a for the synthesis of (C5Me5)2(C5H5)UMe, 5, and (C5Me5)2UMe[CH(SiMe3)2], 6, from KC5H5 and LiCH(SiMe3)2, respectively. Complex 6 is the first example of a mixed alkyl uranium metallocene complex. Sterically induced reduction (SIR) reactivity was not observed with 3-6 although the methyl displacements from the (C5Me5)(1-) ring plane for 3 are the closest observed to date to those of SIR-active complexes. The (1)H NMR spectra of 3 and 4 are unusual in that all of the (C5Me4H)(1-) methyl groups are inequivalent. This structural rigidity is consistent with density-functional theory calculations.     

Reductive reactivity of the organolanthanide hydrides, [(C5Me5)2LnH]x, leads to ansa-allyl cyclopentadienyl (eta(5)-C5Me4CH2-C5Me4CH2-eta(3))2- and trianionic cyclooctatetraenyl (C8H7)3- ligands

The reductive reactivity of lanthanide hydride ligands in the [(C5Me5)2LnH]x complexes (Ln = Sm, La, Y) was examined to see if these hydride ligands would react like the actinide hydrides in [(C5Me5)2AnH2]2 (An = U, Th) and [(C5Me5)2UH]2. Each lanthanide hydride complex reduces PhSSPh to make [(C5Me5)2Ln(mu-SPh)]2 in approximately 90% yield. [(C5Me5)2SmH]2 reduces phenazine and anthracene to make [(C5Me5)2Sm]2(mu-eta(3):eta(3)-C12H8N2) and [(C5Me5)2Sm]2(mu-eta(3):eta(3)-C10H14), respectively, but the analogous [(C5Me5)2LaH]x and [(C5Me5)2YH]2 reactions are more complicated. All three lanthanide hydrides reduce C8H8 to make (C5Me5)Ln(C8H8) and (C5Me5)3Ln, a reaction that constitutes another synthetic route to (C5Me5)3Ln complexes. In the reaction of [(C5Me5)2YH]2 with C8H8, two unusual byproducts are obtained. In benzene, a (C5Me5)Y[(eta(5)-C5Me4CH2-C5Me4CH2-eta(3))] complex forms in which two (C5Me5)(1-) rings are linked to make a new type of ansa-allyl-cyclopentadienyl dianion that binds as a pentahapto-trihapto chelate. In cyclohexane, a (C5Me5)2Y(mu-eta(8):eta(1)-C8H7)Y(C5Me5) complex forms in which a (C8H8)(2-) ring is metalated to form a bridging (C8H7)(3-) trianion.     

Synthesis, structure, and magnetism of an f element nitrosyl complex, (C5Me4H)3UNO

(C(5)Me(4)H)(3)U, 1, reacts with 1 equiv of NO to form the first f element nitrosyl complex (C(5)Me(4)H)(3)UNO, 2. X-ray crystallography revealed a 180° U-N-O bond angle, typical for (NO)(1+) complexes. However, 2 has a 1.231(5) ? N═O distance in the range for (NO)(1-) complexes and a short 2.013(4) ? U-N bond like the U═N bond of uranium imido complexes. Structural, spectroscopic, and magnetic data as well as DFT calculations suggest that reduction of NO by U(3+) has occurred to form a U(4+) complex of (NO)(1-) that has π interactions between uranium 5f orbitals and NO π* orbitals. These bonding interactions account for the linear geometry and short U-N bond. The complex displays temperature-independent paramagnetism with a magnetic moment of 1.36 μ(B) at room temperature. Complex 2 reacts with Al(2)Me(6) to form the adduct (C(5)Me(4)H)(3)UNO(AlMe(3)), 3.     

Synthesis, structure and magnetic behavior of five-coordinate bis(iminopyrrolyl) complexes of cobalt(II) containing PMe3 and THF ligands

The new bis-iminopyrrolyl five-coordinate Co(II) complexes [Co(kappa (2) N, N'-NC 4H 3C(R)N-2,6- (i)Pr 2C 6H 3) 2(PMe 3)] (R = H 3a; Me 3b) were synthesized in high yields (ca. 80-90%), using THF and diethyl ether as solvents, respectively, by (a) treatment of CoCl 2(PMe 3) 2 with the corresponding iminopyrrolyl Na salts ( Ie or If) or (b) reaction of anhydrous CoCl 2 and PMe 3 with Ie or If. A third route was tested, involving the addition of excesses of PMe 3 to the complexes [Co(kappa (2) N, N'-NC 4H 3C(R)N-2,6- (i)Pr 2C 6H 3) 2] (R = H 1e; Me 1f), which was only successful for the synthesis of 3a, in lower yields (ca. 30%). The synthesis of 3b in THF was unfruitful because of the kinetic competition of the solvent, giving rise to mixtures of 1f and its coordinated THF adduct 4b. The synthesis of the new bis-iminopyrrolyl five-coordinate Co(II) complexes [Co(kappa (2) N, N'-NC 4H 3C(R)N-2,6- (i)Pr 2C 6H 3) 2(THF)] (R = H 4a; Me 4b) were carried out in high yields (ca. 80-90%) by the reaction of CoCl 2(THF) 1.5 with the corresponding iminopyrrolyl Na salt. All the compounds have been characterized by X-ray diffraction, with 3a and 3b showing axially compressed trigonal bipyramidal geometry (with the PMe 3 ligand lying on the equatorial plane), whereas complexes 4a and 4b exhibit distorted square pyramidal geometries with the THF molecule occupying the axial position. Complex 4a shows clearly a compressed geometry, but for complex 4b, two polymorphs were characterized, exhibiting molecules with different Co-O (THF) bond lengths, one of them being compatible with an elongated form. Magnetic measurements either in the solid or in the liquid phases indicate that complexes 3a and 3b have low-spin ground states ( S = 1/2). In toluene solution, the geometry is fully confirmed by EPR data, which further indicates a d x (2) - y (2) /d xy ground state. However, compounds 4a and 4b behave unusually because they show magnetic moments that are compatible with high-spin ground states ( S = 3/2) in the solid state, but conform to low-spin ground states ( S = 1/2) when both complexes are dissolved in toluene solutions. The low-spin ground states in toluene solution are confirmed by EPR spectroscopy, which further supports, for complexes 4a and 4b, an axially elongated square pyramidal geometry and a d z (2) ground state. Thus the change in the ground-state and, consequently, in the geometry of complexes 4a and 4b from solid state to toluene solution might be a consequence of the elongation of the Co-O(THF) bond length. DFT studies performed on complexes 3 and 4 corroborate their different structure and magnetic behaviors and verify, for the latter complexes, the structural differences observed in the solid state and in toluene solution.     

(C_5H_9C_5H_4)_3NdBrLi(THF)_3和(C_5H_9C_5H_4)_3SmTHF的合成与结构

无水三氯化钕与环戊烷基环戊二烯钠、溴化锂(1:2:1摩尔比)反应,除去不溶物和溶剂后,产物在己烷/四氢呋喃溶剂中冷冻得到兰紫色晶体(C5H9C5H4)3NdBrLi(THF)3(配合物1)。其中心金属Nd3+的配位数为10,以η5与3个环戊二烯基相连,并通过单溴原子桥连锂原子,形成双核结构。该晶体属三斜晶系,P`1空间群。晶体学参数为a=12.048(2)、b=13.498(3)、c=13.831(3);α=104.16(3)、β=104.07(3)、γ=95.96(3); V=2083.3(7)3、Z=2、Dc=1.35Mg/m3、Mr=847.01gmol-1、F(000)=874。无水三氯化钐与环戊烷基环戊二烯钠(1:3)反应,产物在-30oC下的己烷溶剂中结晶得桔红色晶体(C5H9C5H4)3SmTHF(配合物2)。该晶体属正交晶系,Fdd2空间群。晶胞参数a=28.175(5) 、b=46.24(2)、c=9.167(4);V=11943(8)3、Z=16、Dc=1.38Mg/m3、 Mr=622.11 g·mol-1、F(000)=5136。10配位的金属Sm3+与3个环戊二烯基以η5相连,并结合一个四氢呋喃溶剂分子。     

Reduction of carbodiimides by samarium(II) bis(trimethylsilyl)amides-formation of oxalamidinates and amidinates through C-C coupling or C-H activation

The reaction of [Sm{N(SiMe3)2}2(THF)2] (THF=tetrahydrofuran) with carbodiimides RN=C=NR (R=Cy, C6H3-2,6-iPr2) led to the formation of dinuclear SmIII complexes via differing C-C coupling processes. For R=Cy, the product [{(Me3Si)2N}2Sm(micro-C2N4Cy4)Sm{N(SiMe3)2}2] (1) has an oxalamidinate [C2N4Cy4]2- ligand resulting from coupling at the central C atoms of two CyNCNCy moieties. In contrast, for R=C6H3-2,6-iPr2, H transfer and an unusual coupling of two iPr methine C atoms resulted in a linked formamidinate complex, [{(Me3Si)2N}2Sm{micro-(RNC(H)N(Ar-Ar)NC(H)NR)}Sm{N(SiMe3)2}2] (2) (Ar-Ar=C6H3-2-iPr-6-C(CH3)2C(CH3)2-6'-C6H3-2'-iPr). Analogous reactions of RN=C=NR (R=Cy, C6H3-2,6-iPr2) with the SmII "ate" complex [Sm{N(SiMe2)3Na] gave 1 for R=Cy, but a novel C-substituted amidinate complex, [(THF)Na{N(R)C(NR)CH2Si(Me2)N(SiMe3)}Sm{N(SiMe3)2}2] (3), for R=C6H3-2,6-iPr2, via gamma C-H activation of a N(SiMe3)2 ligand.     

Synthesis and x-ray crystal structure of [(THF)Zn(O(2)(OH)SiR)](4) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))): enroute to larger aggregates

Reaction of aminosilanetriol RSi(OH)(3) (1) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) with diethyl zinc at room temperature in 1:1 stoichiometric ratio affords [(THF)Zn(O(2)(OH)SiR)](4) (2) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) in good yield. The single-crystal X-ray diffraction studies reveal that 2 is monoclinic, P2(1), with a = 17.117(3) A, b = 16.692(5) A, c = 17.399(4) A, alpha = gamma = 90 degrees, beta = 91.45(7) degrees, and Z = 2. The molecular structure of 2 contains two puckered eight-membered Zn(2)Si(2)O(4) rings, which are connected by the Zn-O bonds and form two planar four-membered Zn(2)O(2) rings. Compound 2 contains an unreacted hydroxyl group on each silicon atom, and hence, we carried out the reactions of 2 with dimethylzinc and methyllithium to form [Zn(4)(THF)(4)(MeZn)(4)(O(3)SiR)(4)] (3) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) and [(L)ZnLi(O(3)SiR)](4) (4) (L = 1,4-(Me(2)N)(2)C(6)H(4), R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))), respectively. This suggested that 2 could be an intermediate product formed during the synthesis of 3 and 4.     

Syntheses and solid-state and solution structures of [Ba[(C5Me5)2Ti2F7]2(hmpa)] and [Ba8Ti6F30I2(C5Me5)6(hmpa)6][I3]2

The complexes [Ba[(C5Me5)2Ti2F7]2(hmpa)].(THF), 1.hmpa.(THF), and [Ba8Ti6F30I2(C5Me5)6(hmpa)6][I3]2.10(THF), 2[I3]2.10(THF), were prepared from [Hdmpy](+)[(C5Me5)2Ti2F7]- (dmpy = 2,6-dimethylpyridine), BaI2, and hmpa (hmpa = hexamethylphosphoramide). They were characterized by 1H and 19F NMR and IR spectroscopy and examined by single-crystal X-ray crystallography. The complexation equilibrium of the barium ion in 1 with hmpa and the dynamics of the barium ion moving on the fluorine surfaces of [(C5Me5)2Ti2F7]- in 1.hmpa have been studied by variable-temperature 19F NMR spectroscopy. The core of the complex 2[I3]2.10(THF) resembles the basic structural unit of the cubic perovskite.     

The importance of a single methyl group in determining the reaction chemistry of pentamethylcyclopentadienyl cyclooctatetraenyl uranium metallocenes

The steric factors that allow trivalent [(C(5)Me(5))(3)U] (1) to function as a three-electron reductant with C(8)H(8) to form tetravalent [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-C(8)H(8))] (2) have been explored by examining the synthesis and reactivity of the intermediate, "[(C(5)Me(5))(2)(C(8)H(8))U]" (3), and the slightly less crowded analogues, [(C(5)Me(5))(C(5)Me(4)H)(C(8)H(8))U] and [(C(5)Me(4)H)(2)(C(8)H(8))U], that have, successively one less methyl group. The reaction of [{(C(5)Me(5))(C(8)H(8))U(μ-OTf)}(2)] (4; OTf=OSO(2) CF(3)) with two equivalents of KC(5)Me(5) in THF gave ring-opening to "[(C(5)Me(5))(C(8)H(8))U{O(CH(2))(4)(C(5) Me(5))}]" consistent with in situ formation of 3. Reaction of 4 with two and four equivalents of KC(5)Me(4)H generates two equivalents of [(C(5)Me(5))(C(5)Me(4)H)(C(8)H(8))U] (5) and [(C(5)Me(4)H)(2)(C(8)H(8))U] (6), respectively, which in contrast to 3 were isolable. Tetravalent 5 reduces phenazine and PhEEPh (E=S, Se, and Te) to form the tetravalent uranium reduction products, [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-C(12)H(8)N(2))] (7), [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-SPh)(2)] (8), [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-SePh)(2)] (9), and [{(C(5)Me(5))(C(8)H(8))U}(2)(μ-TePh)(2)] (10), consistent with sterically induced reduction. In contrast, the less sterically crowded 6 does not react with these substrates.     

Synthesis, structure, and 15N NMR studies of paramagnetic lanthanide complexes obtained by reduction of dinitrogen

The recently discovered LnZ3/M and LnZ2Z'/M methods of reduction (Ln = lanthanide; M = alkali metal; Z, Z' = monoanionic ligands that allow these combinations to generate "LnZ2" reactivity) have been applied to provide the first crystallographically characterized dinitrogen complexes of cerium, [C5Me5)2(THF)Ce]2(mu-eta2.eta2-N2) and [(C5Me4H)2(THF)Ce]2(mu-eta2.eta2-N2), so that the utility of 15N NMR spectroscopy with paramagnetic lanthanides could be determined. [(C5Me5)2(THF)Pr]2(mu-eta2.eta2-N2) and [(C5Me4H)2(THF)Pr]2(mu-eta2.eta2-N2) were also synthesized, crystallographically characterized, and studied by 15N NMR methods. The data were compared to those of [(C5Me5)2Sm]2(mu-eta2.eta2-N2). [(C5Me5)2(THF)Ce]2(mu-eta2.eta2-N2) and [(C5Me5)2(THF)Pr]2(mu-eta2.eta2-N2) are unlike their (C5Me4H)1- analogs in that the solvating THF molecules are cis rather than trans. Structural information on precursors, (C5Me4H)3Ce, (C5Me4H)3Pr, and the oxidation product [(C5Me5)2Ce]2(mu-O) is also presented.     

The role of neutral coligands on the stabilization of mono-Tp(i)Pr2 U(III) complexes

The reaction of [UI(3)(THF)(4)] with 1 equiv of KTp()i(Pr)()2 in toluene in the presence of several neutral coligands allowed the synthesis of a novel family of mono-Tp()i(Pr)()2 complexes, [UI(2)Tp()i(Pr)()2(L)(x)()] [L = OPPh(3), x = 1 (3); L = C(5)H(5)N, x = 2 (4); L = Hpz()t(Bu,Me), x = 2 (5); and L = bipy, x = 1 (6)]. The adduct with THF, [UI(2)Tp()i(Pr)()2(THF)(2)(-)(3)] (1), could also be isolated by reacting [UI(3)(THF)(4)] with 1 equiv of KTp()i(Pr)()2 in tetrahydrofuran. However, complex 1 is not a good starting material to enter into the mono-Tp()i(Pr)()2 U(III) complexes as it decomposes in solution, leading to mixtures of U(III) species coordinated with Hpz()i(Pr)()2. The solid-state structures of 3, 4, and 6 were determined by single-crystal X-ray diffraction and revealed that this family of mono-Tp()i(Pr)()2 complexes can be six- (3) or seven-coordinated (4 and 6), depending on the nature of the neutral coligand. Complex 3 displays distorted octahedral coordination geometry, while 4 and 6 display distorted pentagonal bipyramid and capped octahedral geometries, respectively. Complexes 3 and 6 are static in solution, and the patterns of the (1)H NMR spectra are consistent with the C(s)() symmetry found in the solid state. The other complexes (1, 4, and 5) are fluxional, but the dynamic processes involved can be slowed by decreasing the temperature.