A heteroatom-stabilized neutral imine organoactinide complex: x-ray structure of dichlorobis(pentamethylcyclopentadienyl)uranium(IV) phosphine imine

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

“…This geometry resembles that in Cp* 2 UCl 2 (HNPPh 3 ), Cp* 2 UCl 2 (HNSPh 2 ) and [Cp à (Cl)(HNSPh 2 )U(l 3 -O)(l 2 -O) 2 U(Cl) (HNSPh 2 ) 2 ] 2 where N-H---Cl hydrogen bonding is proposed [14,18].…”

“…By )60°C the former two are resolved into three resonances at )0.5, )2.0 and )15.1 ppm that can be assigned to the aromatic protons on the phenyl groups. The resonance at )163 ppm is assigned to the N-H proton by analogy to the value of )142 ppm observed in Cp* 2 UCl 2 (HNSPh 2 ) [18]. Based on this assignment, the O-H proton resonance was not located.…”

“…The heavy atom structure of Cp* 2 UCl(OH)(HNSPh 2 ) is very similar to Cp* 2 UCl 2 (HNSPh 2 ) [18] with the former being derived from the latter by the substitution of a hydroxide for a chloride. The bond distances and angles within the Cp* 2 U and U-N(H)SPh 2 moieties are unremarkable and lie in the same range as those in Cp* 2 UCl 2 (HNSPh 2 ), Cp* 2 UCl 2 (HNPPh 3 ) and [Cp à (Cl)(HNSPh 2 )U(l 3 -O)(l 2 -O) 2 U(Cl) (HNSPh 2 ) 2 ] 2 [14,18]. Placing the imino hydrogen at its calculated position, it is directed towards the chloride.…”

Synthesis and reactions of (η5-C5Me4-2-C5H4N)2UCl2 and its derivatives, including the puzzling formation of the ansa-metallocene C2H4(η5-C5Me3-2-C5H4N)2UCl2

“…1.65 and 0.45 Å and 73 , respectively). The UeCl distance of 2.6874(16) Å can be compared with the average value of 2.69(5) Å in (Cp*) 2 UCl 2 (HNPPh 2 ) (Cp* ¼ h 5 -C 5 Me 5 ) [7].…”

Mononuclear Carbene Dithiolate [Ni(NHX)(′S2C ′)] Complexes with HNX = HNPiPr3 or HNSPh2 Coligands (′S2C ′2- = 1,3-ImidazolidinylN,N′-bis(2-benzenethiolate)(2-))

“…This is readily rationalized in molecular orbital terms by two unpaired electrons occupying antibonding orbitals in 3. [12]. IR spectra and X-ray structure determinations both support the existence of intramolecular N±H´´´S-(thiolate) hydrogen bonds in 1 and 2.…”