Uranium-sulfilimine chemistry. Hydrolysis of Cp*2UCl2 with HNSPh2·H2O and the crystal structure of Cp*2UCl(OH)(HNSPh2), a metallocene terminal hydroxy complex of tetravalent uranium

Stabilization of U(III) to Oxidation and Hydrolysis by Encapsulation Using 2.2.2-Cryptand

“…In 4-U , 5-U , and 6-U , the U­(III) ion adopts a tetra-capped trigonal prismatic geometry similar to those in 1-U , 2-U , and 3-U and in other previously reported lanthanide-in-crypt complexes. ,,, The ranges of U–N­(crypt) and U–O­(crypt) distances in 4-U , 5-U , and 6-U overlap with those previously reported for 1-U , 2-U , and 3-U . The 2.515(3)–2.519(3) Å U–O­(H 2 O) distances in 5-U and 6-U are also similar to previously reported U­(III)–O­(OH 2 ) distances, − and they are significantly longer than reported U­(IV)–O­(OH) bonds of 2.040(2)–2.137(7) Å. − …”

Synthesis and Structure of the Bis(tetramethylcyclopentadienyl)uranium Metallocenes (C5Me4H)2UMe2, (C5Me4H)2UMeCl, [(C5Me4H)2U][(μ-η6:η1-Ph)(μ-η1:η1-Ph)BPh2], and [(C5Me4)SiMe2(CH2CHCH2)]2UI(THF)

“…The THF was removed by rotary evaporation to afford 6 as a green solid (312 mg, 96%). X-ray-quality crystals of 6 formed from a saturated solution of hexanes at -35 °C within 24 (2). A red crystal of approximate dimensions 0.24 × 0.26 × 0.33 mm was mounted on a glass fiber and transferred to a Bruker CCD platform diffractometer.…”

“…The discovery of this complex led to an extensive development of bis-(pentamethylcyclopentadienyl)uranium chemistry that continues today. [1][2][3][4][13][14][15][16][17][18][19][20][21][22][23][24][25][26] The uranium chemistry of (C 5 Me 4 H)has received much less attention than that of ( Until recently, the focus was entirely on tris(tetramethylcyclopentadienyl) species of the general formulas (C 5 Me 4 H) 3 U, 27,28 (C 5 Me 4 H) 3 UL (L ) neutral ligand), [27][28][29] and (C 5 Me 4 H) 3 UX (X ) anion). 27,28,30,31 Although the (C 5 Me 4 H)ligand has delivered interesting chemistry in tris(cyclopentadienyl)uranium systems, [27][28][29][30][31] its bis-(cyclopentadienyl)uranium chemistry has not been extensively developed.…”

“…A major breakthrough in uranium metallocene chemistry occurred in 1978, , when Marks and co-workers showed that the (C 5 Me 5 ) - ligand could be used to isolate a bis(cyclopentadienyl)uranium complex, (C 5 Me 5 ) 2 UCl 2 , that was stable to ligand redistribution. The discovery of this complex led to an extensive development of bis(pentamethylcyclopentadienyl)uranium chemistry that continues today. − ,− …”

Reaction Chemistry of the U3+ Metallocene Amidinate (C5Me5)2[iPrNC(Me)NiPr]U Including the Isolation of a Uranium Complex of a Monodentate Acetate

“…The U−(C 5 Me 5 ring centroid) distances of 2.495 and 2.504 Å and the U−N(1) and U−N(2) distances of 2.503(3) and 2.370(3) Å in 7 (Table ) are not unusual: they are similar to those observed in 2 (2.482(3) and 2.380(3) Å) and 6 (2.480(3) and 2.371(4) Å). The 2.213(2) Å U−O(1) bond is similar to the 2.117(9) Å of the U−O(OH) bond in (C 5 Me 5 ) 2 UCl(OH)(HNSPh 2 ), but much shorter than the average U−O(acetate) bond distance of 2.41(1) Å in [HB(3,5-Me 2 Pz) 3 ]U(O 2 CMe) 3 , in which the acetates are coordinated in a bidentate fashion. The 1.302(4) and 1.221(4) Å bond distances for C(29)−O(1) and C(29)−O(2), respectively, show the localization in the acetate ligand.…”