Fulvalene titanium and zirconium complexes: synthesis and NMR study of phosphanido-, alkyl-, and alkynyl-derivatives. X-ray crystal structures of [{ Ti(η5-C5 H 5)(μ-PPh2)}2{μ-(η5-C5H4-η5-C5H4)}] and [{Zr(η5-C5H5)(μ-C=CSiMe3)}2{μ-( η5-C5H4-η5-C5H4)}]
Authors
Cano Sierra, Ana María; Cuenca Agreda, Tomás; Galakhov, Mikhail V.; Rodríguez Centeno, Gema María; Royo Gracia, Pascual; [et al.]Identifiers
Permanent link (URI): http://hdl.handle.net/10017/4586DOI: 10.1016/0022-328X(94)05288-M
ISSN: 0022-328X
Publisher
Elsevier
Date
1995Funders
We gratefully acknowledge financial support from DGICYT (Project 92-0178-C) for this research. A.C. acknowledges MEC for a Fellowship.
Bibliographic citation
Journal of Organometailic Chemistry, 1995, v. 493, p. 17-25
Keywords
Titanium
Zirconium
μ-Phosphanido
Alkynyl
Fulvalene
Alkyl
Project
92-0178-C (Ministerio de Ciencia y Tecnología)
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1016/0022-328X(94)05288-MRights
(c) Elsevier, 1995
Access rights
info:eu-repo/semantics/openAccess
Abstract
Reaction of [{M(1/-C5H 5Xµ-Cl)}z{µ-( 175-C5H 4-175-C5H 4 )}] (M = Ti, 1; Zr, 2) or ({M( 175-C5H 5)Cl 2}z{µ-(175-C5H 4-175-C5H 4)}],
(M = Ti, 5; Zr, 6) with one or two equivalents of LiPPh 2 afforded the new phosphanidometal(III) complexes [{M(C5H 5Xµ PPh2)h{µ-(175-C5H4- 175-C5H4)}], (M = Ti, 3; Zr, 4). Reaction of 2 with LiO:CSiMe 3 led to the diamagnetic zirconium(III)
alkynyl derivative [{Zr(C5H 5Xµ-O:CSiMe 3)}z(µ-175-C5H 4-175-C5H 4 ], 7. Alkylation of 6 with LiCH 2CMe2 Ph gave [{Zr(175- C5H5XCH2CMe2Ph)2}z{µ-( 175-C5H 4-175-C5H 4)}], 8. A detailed NMR study of complexes 3 and 4 allowed the observation of the spectral behaviour of the eight different fulvalene protons through their coupling to the 31P nucleus. The fluxional behaviour of
complex 7 was studied by dynamic DNMR, and kinetic parameters for the σ-Π-conversion of the alkynyl ligand were detem1ined. The molecular structures of complexes 3 and 7 were determined by X-ray diffraction methods.
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