Terminal oxo, sulfido, selenido, and tellurido complexes of zirconium, ([eta][sup 5]-C[sub 5]Me[sub 4]R)[sub 2]Zr(E)(NC[sub 5]H[sub 5]). Comparison of terminal Zr-E single and Zr=E double bond lengths

摘要: The series of terminal zirconium chalcogenido complexes ([eta][sup 5]-C[sub 5]Me[sub 4]R)[sub 2]Zr(E)(NC[sub 5]H[sub 5])(E = O, S, Se, Te; R Me, Et) has been synthesized by the reactions 2](CO)[sub 2] with either N[sub 2]O or elemental chalcogen (E S,Se,Te) in presence NC[sub 5]. tellurido complex 5])[sub 2]Zr(Te)(NC[sub 5]) reacts instantaneously to give oxo derivative 2]Zr(O)(NC[sub 5]). hydrochalcogenido derivatives 2]-Zr(EH) [l brace][eta][sup 1]-OC(Ph)=CH[sub 2][r brace] have obtained PhC(O)CH[sub 3], thus demonstrating basicity ligands these complexes. structures ([eta][sub 4]Et)[sub 2]Zr(E)NC[sub 5] Te) and 2]Zr(EH) Se) determined X-ray diffraction, thereby allowing a comparison Zr-E single Zr=E double bond lengths be made for structurally-related compounds. A consideration difference M-E M=E bonds,more » respect covalent radii chalcogens, leads conclusion that radius [([eta][sup 5]R[sub 2]Zr] system is ca. 0.07 [angstrom] shorter than its radius. For heavier chalcogens (S, Te), Zr--E may predicted reasonably well on basis sum Zr E. In contrast, both - O are anomalously short. 47 refs., 12 figs., 13 tabs.« less