Activation of phosphorus by group 14 elements in low oxidation states

The activation of phosphorus remains a popular and competitive area of research driven by the dual goals of finding ways to avoid the environmentally questionable P-Cl compounds applied in many industrial processes and the target of catalytic functionalization of P(4). In recent years the activation, degradation, fragmentation, and functionalization of white phosphorus by compounds with heavier main group elements have become a fertile area of research. The isolation of various carbenes and functionalized silylenes has prompted chemists to investigate their reactions with white phosphorus. The most intriguing fact in these reactions is the subtle change in the substituents may afford strikingly different compounds. For example, from the reaction of P(4) with PhC(NtBu)(2)SiCl a cyclic Si(2)P(2) derivative is obtained, whereas the analogous reaction with PhC(NtBu)(2)SiN(SiMe(3))(2) resulted in an acyclic Si(2)P(4) framework. Similar phenomena have also been observed in the carbene mediated P(4) activation. Apart from these, a new entry point into phosphorus chemistry is the gentle activation of P(4) by an alkyne analogue of tin. In this feature article we have covered the activation of phosphorus by compounds with low valent group 14 elements with special concern to the recent developments in this topic.     

1H,89Y HMQC and Further NMR Spectroscopic and X‐ray Diffraction Investigations on Yttrium‐Containing Complexes Exhibiting Various Nuclearities

2D ¹H,⁸⁹Y heteronuclear shift correlation through scalar coupling has been applied to the chemical‐shift determination of a set of yttrium complexes with various nuclearities. This method allowed the determination of ⁸⁹Y NMR data in a short period of time. Multinuclear NMR spectroscopy as function of temperature, PGSE NMR‐diffusion experiments, heteronuclear NOE measurements, and X‐ray crystallography were applied to determine the structures of [Y₅(OH)₅(L ‐Val)₄(Ph₂acac)₆] ( 1 ) (Ph₂acac=dibenzoylmethanide, L ‐Val=L ‐valine), [Y( 2 )(OTf)₃] ( 3 ), and [Y₂( 4 )(OTf)₅] ( 5 ) ( 2 : [(S)P{N(Me)N?C(H)Py}₃], 4 : [B{N(Me)N?C(H)Py}₄]^?) in solution and in the solid state. The structures found in the solid state are retained in solution, where averaged structures were observed. NMR diffusion measurements helped us to understand the nuclearity of compounds 3 and 5 in solution. ¹H,¹⁹F HOESY and ¹⁹F,¹⁹F EXSY data revealed that the anions are specifically located in particular regions of space, which nicely correlated with the geometries found in the X‐ray structures.     

Synthesis and characterization of β-diketiminate germanium(II) compounds

Reactions of LGeCl (L = CH[C(Me)N(Ar)](2); Ar = 2,6-iPr(2)C(6)H(3)) with KOtBu or LiR (R = 2-thienyl, N(H)Ar, PPh(2)) yielded the germanium(II) compounds LGeR [R = OtBu (1), 2-thienyl (2), N(H)Ar (3), PPh(2) (4)]. The reduction of (2-thienyl)(2)PCl with lithium afforded the diphosphane [(2-thienyl)(2)P](2) (5). The treatment of (2-thienyl)(2)PCl with LiAlH(4) or KHBtBu(3) led to the formation of (2-thienyl)(2)PH (6). The NHC-assisted reaction of LGeCl and 6 resulted in the isolation of LGeP(2-thienyl)(2) (7). This is the first example where NHC is used for eliminating HCl from compounds with P-H and Ge-Cl bonds. All solid products were characterized by elemental analysis, NMR and IR spectroscopy, and single-crystal X-ray structure determination.     

Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application

Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity.