Syntheses of the Phenylchalcogenolate Complexes (.eta.5-C5Me5)2Zr(EPh)2 (E = O, S, Se, Te) and (.eta.5-C5H5)2Zr(OPh)2: Structural Comparisons within a Series of Complexes Containing Zirconium-Chalcogen Single Bonds

Abstract

The complete series of phenylchalcogenolate derivatives of permethylzirconocene Cp*2Zr(EPh)2 (Cp* = z/5-C;-Mes; E = O, S, Se, Te) has been prepared by the reactions of Cp*2Zr(CO)2 with PhOH and Ph2E2 (E = S, Se, Te). The molecular structures of all of the derivatives Cp*2Zr(EPh)2 have been determined by X-ray diffraction, thereby providing evidence that the nature of the bonding varies as a function of the chalcogen. Specifically, the structure of the phenoxo derivative is notably distinct from those of its heavier congeners. For example, whereas the Zr-S, Zr-Se, and Zr-Te bond lengths are comparable to the sum of their respective covalent radii, the Zr-O bond length is significantly shorter than the sum of the covalent radii, as would be anticipated due to an increased ionic contribution to the bonding. In addition, the Zr-O-C bond angle [172.7(2)°] in Cp*2-Zr(OPh)2 is effectively linear, whereas the Zr-E-C bond angles for the heavier congeners are significantly bent [113°-119°]. Comparison of the structure of Cp*2Zr(OPh)2 with that of the less substituted zirconocene derivative Cp2Zr(OPh)2, which possesses a bent Zr-O-C moiety [147(1)°], suggests that the linearity of Cp*2Zr- (OPh)2 may be attributed to steric factors. Thus, short M-OR bond lengths and linear M-O-R angles are not necessarily a consequence of strong -djr lone pair donation from oxygen to the metal. Cp*2Zr(OPh)2 is monoclinic: C2Jc (No. 15), a = 11.049( 2) k,b= 15.445(3) A, c = 17.141(3) Á, ß = 104.24(1)°, and Z = 4. Cp*2Zr(SPh)2 is monoclinic: C2/c (No. 15), a = 14.444(4) k,b= 11.449(2) A, c = 18.262(3) Á, ß = 103.39-(2)°, and Z = 4. Cp*2Zr(SePh)2 is hexagonal: P6\ (No. 169), a = 12.903(2) A, c = 31.923(6) A, and Z = 6. Cp*2Zr(TePh)2 is monoclinic: P2,/c (No. 14), a = 16.917(3) k,b = 25.326(6) A, c = 15.234(4) A, ß = 107.95-(2)°, and Z = 8. Cp2Zr(OPh)2 is orthorhombic: Aba2 (No. 41), a = 8.274(3) k,b= 19.843(9) A, c = 11.586-(8) A, and Z = 4.

Synthese, Struktur und Charakterisierung von Titan-, Zink-, Nickel- und Palladium-Thioether-Thiolat-Komplexen heterocyclischer 1,2-Dithiolate

“…Zur Komplexierung wurden koordinativ halbgesa È ttigte Metallhalogenide wie Dichloro-di(methylcyclopentadienyl)-titan (Cp' 2 [9]. Die ra È umliche Orientierung der Thiolatliganden [10]. Die gefundenen Winkel S1± Ti±S5±C5 von 61,7°und S5±Ti±S1±C1 von 68,5°besta È-tigen dies und sind vergleichbar mit bisher beschriebenen, wie z.…”

Reactivity of a Dititanium Bis(pentalene) Complex toward Heteroallenes and Main-Group Element–Element Bonds

“…44,45 With highly reducing metal complexes EE bond cleavage of the dichalcogenide routinely occurs to yield a complex bearing the respective chalcogenoate (RE) − ligands.…”

Synthesis and characterization of bis(indenyl) zirconium aryloxide derivatives and their use in α‐olefin polymerization

“…Attempts to grow crystals of these complexes from various solvents for X-ray diffraction studies were unsuccessful. However, the complete NMR characterization ( 1 H, 13 C and heteronuclear multiple quantum coherence (HMQC)) provided an unambiguous identification, as illustrated in Table 1. Examining the data in Table 1, it seems that the proton H a on the five-membered ring of the indenyls is the most sensitive to the nature of the s-ligands.…”

“…(Z 5 -C 5 Me 5 ) 2 Zr(OPh) 2 and (Z 5 -C 5 H 5 ) 2 Zr(OPh) 2 were synthesized by Howard et al, who investigated the nature of the zirconium-oxo interaction by structural analyses. 13 Later, a series of bis(phenoxy) derivatives of Cp 2 ZrCl 2 with different phenoxy steric-demanding groups was prepared by Repo et al and used in ethene polymerization with MAO. 14 We have also synthesized some new bis(indenyl) zirconium diaryloxide compounds, choosing the indenyl ligand to study the effect of this complexing group on the polymerization behaviour of these compounds when activated with MAO.…”