Formation of Novel P-Functionalized Ligands by Insertion Reactions of RNCX (R = Ph, X = O, S; R = Prⁱ, X = O) into the Zr−P Bond of [Cp°₂ZrCl(PHCy)] (Cp° = η⁵-C₅EtMe₄, Cy = Cyclohexyl) and [Cp‘₂ZrCl{PH(TRIP)}] (Cp‘ = η⁵-C₅MeH₄, TRIP = 2,4,6-Prⁱ₃C₆H₂)

Abstract

Cp°2ZrCl(PHCy)] (1; Cp°) η 5 -C 5 EtMe 4 , Cy ) cyclohexyl) and [Cp′ 2 ZrCl{PH(TRIP)}] (2; 8)). 3-8 were characterized spectroscopically (IR, NMR, MS), and crystal structure determinations on 4-6 showed an η 2 bonding mode (X,N) of the XC(PHR′)NR (R′ ) Cy, TRIP) ligands. Of the two possible coordination modes of the ligand, 4 and 5 are obtained exclusively as the endo isomer, in which the NR group is adjacent to the Zr-Cl bond, while for 6-8, both isomers (endo and exo) are formed (1:8 (6), 1:30 (7) and 1:5 (8)), whereby the exo isomer is favored. The exo isomer of 6 was structurally characterized.

Insertion of ketenes into lanthanocene n-butylamide and imidazolate complexes

“…1). A C@N stretching frequency in the IR spectrum at approximately 1580 cm À1 is in agreement with the bidentate g 3 -bonding mode of the amido ligand [10]. The mass spectra of 1 and 2 displays a series of peaks representing fragments derived from the parent molecules and are characterized by the [M/2-Cp].…”

Reactivity of Lanthanocene Amide Complexes toward Ketenes: Unprecedented Organolanthanide‐Induced Conjugate Electrophilic Addition of Ketenes to Arenes

“…The bonding mode of the resulting amido ligand was verified by the X‐ray analysis of complexes 5 a and 5 b (Figure 3). A CN stretching frequency in the IR spectrum at approximately 1580 cm −1 is in agreement with the bidentate η 3 ‐bonding mode of the amido ligand,36 and is significantly lower than those of monodentate amido ligands 9. Also, the NH stretching band that appeared at about 3300 cm −1 in the IR spectrum of [{Cp 2 LnNHPh} 2 ] was no longer present 37…”

Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as “P−” anion sources

“…In the latter systems, the insertion of isocyanates into the metal-phosphorus bond has been observed. [9][10][11] Some yttrium-phosphido complexes were found to catalyze the cyclo-trimerization of isocyanates, 9 however, relatively high catalyst loadings are required to reach full conversion.…”